Aqueous crosslinkable resin dispersions, method of their production and use thereof

ABSTRACT

The present invention yields a coating film excellent in adhesion, water resistance, solvent resistance and durability. A compound having a carboxyl group and a long-chain alkylthio group or a salt thereof is used as an emulsifier and emulsion polymerization is carried out using a polymerizable monomer or monomers having, within their molecule, a group reactive with a carboxyl group as raw materials for emulsion polymerization, whereby the resin produced by emulsion polymerization and the emulsifier react with each other efficiently on the occasion of film formation and form a crosslinked structure. When a compound having a polymerizable unsaturated group in addition to the carboxyl group and long-chain alkylthio group or a salt thereof is used as the emulsifier, not only the above-mentioned crosslinked structure is formed but also the polymerizable unsaturated group in the emulsifier will react with the unsaturated group in the polymerizable monomer or monomers in the manner of grafting. As a result, the compatibility between the emulsifier and the emulsion-polymerized resin is improved.

This is a division of application Ser. No. 07/257,746, filed on Oct. 14,1988, U.S. Pat. No. 5,087,603.

BACKGROUND OF THE INVENTION

This invention relates to aqueous resin dispersions in which the resinproduced by emulsion polymerization can for crosslinks together with theemulsifier used, to a method of producing the same and to an applicationthereof.

Hithertofore, aqueous dispersions of vinyl polymers, such as acrylic,vinyl acetate, styrene-butadiene and like polymers, have been widelyused in various industrial fields as coating compositions or binders,for instance. These dispersions are advantageous in that since they areaqueous, the toxicity and fire hazards due to organic solvents arelittle with said dispersions. Accordingly, the sphere of theirapplication is expanding more and more. On the other hand, with theexpansion of their fields of use, they are more and more required tohave diversified and higher-level performance characteristics. The priorart aqueous dispersions cannot fully meet such current requirements anylonger and therefore their range of application is limited.

To cope with these circumstances, studies are under way to improve theperformance characteristics of emulsions. Various means have beenproposed for improving the performance characteristics of emulsions. Asone of them, there may be mentioned the method which comprisesconverting films obtained from an emulsion to three-dimensionalcrosslinked ones. For instance, Shikaze has proposed [Japanese KokaiTokkyo Koho (Published Unexamined Patent Application) No. 52-72731] acoating composition crosslinkable at low temperatures which contains, asa coat film-forming component, a copolymer produced by emulsioncopolymerizing

(A) at least one water-soluble monomer having one or more carboxylgroups,

(B) at least one oil-soluble monomer having two or more vinyl or allylgroups,

(C) N-methylolacrylamide and

(D) at least one monomer copolymerizable with these monomers.

This composition indeed forms a crosslinked coat film and has goodsolvent resistance but is unsatisfactory in water resistance because ofthe use, as the emulsifier for emulsion polymerization, of alow-molecular-weight emulsifier which is in general use. Anotherdisadvantage is that toxic formalin is generated on the occasion ofcrosslinking.

In Japanese Kokai Tokkyo Koho No. 62-25163, an aqueous copolymerdispersion composition is proposed, which is prepared by adding amacromolecular hydrazine derivative which has at least two carbazoylgroups per molecule and is sparingly soluble in water to an aqueousdispersion of an aldehyde or ketone group-containing copolymer.

This composition can be crosslinked at low temperatures and gives partlyimproved performance characteristics. However, the emulsifier foremulsion polymerization as used there is a general-purposelow-molecular-weight and therefore said composition still has theproblem of foaming due to the emulsifier as well as the drawback ofunsatisfactory water resistance.

Japanese Kokai Tokkyo Koho No. 60-37801 proposes a method of improvingthe emulsion performance, namely:

A method of producing an aqueous vinyl resin dispersion for coatingpurposes which comprises polymerizing an ethylenically unsaturatedmonomer in an aqueous medium in the presence of a vinyl copolymercontaining, within its molecule, 5-40% by weight of a unit of theformula ##STR1## wherein R₁, R₂ and R₃ each independently is hydrogen oralkyl and n is 2 to 20, and having an acid value of 30-200 mg KOH/g,said vinyl copolymer being in the neutralized state.

Japanese Patent Publication No. 60-42249 proposes the following:

A method of producing an aqueous polymer dispersion which comprisesradical copolymerizing 0.1-10% by weight of one or moreα,β-ethylenically unsaturated monomers having a sulfo substituent and90-99.9% by weight of one or more other α,β-ethylenically unsaturatedmonomer in an aqueous medium in the presence of a water-soluble oralkali-soluble oligomer derived from an α,β-ethylenically unsaturatedmonomer and having a terminal alkylthio group and a molecular weight of200-5,000.

Furthermore, Japanese Kokai Tokkyo Koho No. 61-111136, Japanese KokaiTokkyo Koho No. 61-130376, Japanese Kckai Tokkyo Koho No. 61-7368,Japanese Kokai Tokkyo Koho No. 61-136560 and Japanese Kokai Tokkyo KohoNo. 61-133137 propose the following:

A method of producing an emulsion which comprises emulsioncopolymerizing a monomer or monomers using as the emulsifier an oligomeror oligomers of the general formula (1) and/or (2) ##STR2## wherein R₁is straight-chain primary alkyl or branched primary or secondary alkylcontaining 6-16 carbon atoms, or a mixture of these, R₂ to R₅ eachindependently is hydrogen, carboxyl, carboxymethyl or alkyl of 1 to 5carbon atoms, or ammonium base, amine base, alkali metal base oralkaline earth metal base thereof, R₆ is hydrogen, halogen or alkyl, Xis cyano or --COOCH₃, Y is hydrogen, ammonium, amine base, alkali metalor alkaline earth metal, and a and b each independently is a number of1-100; as well as an adhesive composition, an adhesive for carpetlining, and an adhesive to be applied to fibrous base materials, eachcontaining said emulsion.

As compared with the use of a low-molecular-weight emulsifier such assodium dodecylbenzenesulfonate or nonylphenol-ethylene oxide adduct, theuse of the above-mentioned polymer emulsifier or oligomer emulsifier isadvantageous, for example, in that foaming is slight and that the waterresistance can be improved. However, these techniques allow thehydrophilic polymer used as the emulsifier to remain in films after filmformation without reacting in any way. Accordingly, such performancecharacteristics as water resistance are still impaired although theextent of impairment is less as compared with those low-molecular-weightemulsifiers which are in general use.

As mentioned above, the known techniques or methods each still has adrawback or drawbacks or fails to afford satisfactory performancecharacteristics.

SUMMARY OF THE INVENTION

It is an object of the invention to provide an aqueous crosslinkableresin dispersion capable of self-crosslinking, after evaporation ofvolatile components, rapidly and even at low temperatures to give a coatfilm excellent in adhesion, water resistance, solvent resistance,durability and so forth, a method producing such dispersion and a use ofsuch dispersion.

The above and other objects can be accomplished by providing an aqueouscrosslinkable resin dispersion characterized by its being obtained byemulsion-polymerizing in an aqueous medium a monomer composition [I]composed of 0.1-40% by weight of at least one polymerizable monomer (a)having, within its molecule, a group reactive with a carboxyl group and60-99.9% by weight of one or more other polymerizable monomer (b) [thesum total of the polymerizable monomers (a) and (b) being 100% byweight] in the presence of a water-soluble or water-dispersibleemulsifier or emulsifiers selected optionally from one or both of thegroups (P) and (Q) mentioned below:

(P) Polymers [IIa] having a terminal alkylthio group and an acid valueof not less than 200 as obtained by polymerizing a polymerizable monomercomposition [A] containing an unsaturated carboxylic acid as anessential component thereof in the presence of an alkylmercaptan [B]having 6 to 18 carbon atoms; and/or salts thereof;

(Q) Polymers [IIb] having a terminal alkylthio group and an acid valueof not less than 200 as obtained by polymerizing a polymerizable monomercomposition [A] containing an unsaturated carboxylic acid as anessential component thereof in the presence of an alkylmercaptan [B]having 6 to 18 carbon atoms and further reacting the resulting polymerwith a polymerizable monomer (c) having, within its molecule, a groupreactive with a carboxyl group; and/or salts thereof.

The above and other objects can also be accomplished by providing amethod of producing aqueous crosslinkable resin dispersions whichcomprises emulsion-polymerizing in an aqueous medium a monomercomposition [I] composed of 0.1-40% by weight of at least onepolymerizable monomer (a) having, within its molecule, a group reactivewith a carboxyl group and 60-99.9% by weight of one or more otherpolymerizable monomer (b) [the sum total of the polymerizable monomers(a) and (b) being 100% by weight] in the presence of a water-soluble orwater-dispersible emulsifier or emulsifiers selected optionally from oneor both of the groups (P) and (Q) mentioned above.

The aqueous crosslinkable resin dispersions according to the presentinvention and compositions derived from said dispersions by adding ametal oxide, a water-soluble resin and/or the like can be used, eitheras they are or after further addition of additives, such as crosslinkingagents, fillers, heat-sensitive color-developing components andpressure-sensitive color-developing components, as coating compositions,textile-finishing compositions, adhesives, coating compositions forheat-sensitive color-developing layer formation, coating compositionsfor pressure-sensitive color-developing layer formation, andcompositions to be used in other fields of application.

DETAILED DESCRIPTION OF THE INVENTION

The polymers, inclusive of salts thereof, belonging to the groups (P)and (Q), which are used as emulsifiers in accordance with the presentinvention and are produced by using the above-mentioned materials,should have an acid value of not less than 200 so that the emulsifiedsystem can have a sufficient degree of stability during emulsionpolymerization and that the water resistance, solvent resistance,strength and other characteristics can be secured when coat films areformed from the resin produced. Said polymers preferably have amolecular weight of within the range 300-7,000, in particular within therange of 400-4,000. When the molecular weight is outside this range, theemulsion stability may become insufficient or the resin coat filmsobtained may be not excellent in all the respects, namely, waterresistance, solvent resistance and strength.

In the following, the polymerizable monomer composition [A] containingan unsaturated carboxylic acid as an essential component thereof, thealkylmercaptan [B], and the radical polymerization initiator, which areused in the synsthesis of the polymer [IIa] or [IIb], as well as thepolymerizable monomer or monomers (c) having, within their molecule, agroup reactive with a carboxyl group, which is to be used in thesynthesis of the polymer [IIb], are described in further detail.

The unsaturated carboxylic acid provides the polymer [IIa] or [IIb] withhydrophilic property by introducing a carboxyl group thereinto. Saidcarboxyl group serves as a functional group in crosslinking the resinobtained by emulsion polymerization of the monomer composition [I] bymeans of said polymer [IIa] and/or [IIb]. The unsaturated carboxylicacid is not limited to any particular species if it has a carboxyl groupand a polymerizable unsaturated group within its molecule. As examplesof such unsaturated carboxylic acid, there may be mentioned, forexample, unsaturated monocarboxylic acids, such as (meth)acrylic acidand crotonic acid; unsaturated polybasic carboxylic acids, such asmaleic acid, fumaric acid and itaconic acid; and monoester compoundsderived from these unsaturated polybasic carboxylic acids and monohydricalcohols. These may be used either singly or as a mixture of two ormore.

While the polymerizable monomer composition [A] may consist of anunsaturated carboxylic acid alone, one or more other polymerizablemonomers may be used in combination as necessary. Usable polymerizablemonomers are not limited to any particular species provided that theyare copolymerizable with the unsaturated carboxylic acid. Thus, mentionmay be made of styrene and styrene derivatives, such as vinyltoluene,α-methylstyrene, chloromethylstyrene, styrenesulfonic acid and saltsthereof; (meth)acrylamide and (meth)acrylamide derivatives, such asN-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide,N-methylolacrylamide and N,N-dimethyl(meth)acrylamide; (meth)acrylicacid esters synthesized by esterification of (meth)acrylic acid with C₁-C₁₈ alcohols, such as methyl (meth)acrylate, ethyl (meth)-acrylate andbutyl (meth)acrylate; hydroxyl group-containing (meth)acrylic acidesters, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate and monoesters of (meth)acrylic acid and polypropyleneglycol or polyethylene glycol; 2-sulfoethyl (meth)acrylate and saltsthereof, vinylsulfonic acid and salts thereof, (meth)acrylonitrile, andso forth. These may be used either alone or in the form of a mixture oftwo or more. The polymerizable monomers other than the unsaturatedcarboxylic acid can modify the compatibility between the emulsifierobtained by polymerizing the polymerizable monomer or monomers [A] andthe polymer component obtained by emulsion-polymerizing the monomercomponents in the presence of said emulsifier, the crosslinkability ofsaid polymer component with said emulsifier, and thehydrophilic-hydrophobic balance of said emulsifier. Therefore, when oneor more polymerizable monomers other than the unsaturated carboxylicacid are used, it is necessary to determine their kind and amountcarefully in due consideration of the above facts. As for their amount,they should be used in an amount such that the polymer [IIa] or [IIb]can have an acid value of not less than 200. Acid values below 200 areundesirable because the performance of said polymers as emulsifiersand/or the crosslinkability of the aqueous crosslinkable resindispersion is decreased at such acid values.

The alkylmercaptan [B] is used for the purpose of rendering the polymer[IIa] or [IIb] surface-active by introducing into it a terminalalkylthio group. Alkylmercaptans having 5 carbon atoms or 19 or morecarbon atoms cannot be used since such alkylmercaptans may impair theemulsion stability during emulsion polymerization and the storagestability. The alkylmercaptan [B] should be used in an amount selecteddepending on the desired molecular weight of the polymer [IIa] or [IIb].Generally, however, it is preferably used in an amount within the rangeof 2-300 parts by weight per 100 parts by weight of the polymerizablemonomer composition [A]. As examples of such alkylmercaptan [B], theremay be mentioned n-hexylmercaptan, n-octylmercaptan, n-dodecylmercaptan,t-dodecylmercaptan, cetylmercaptan and stearylmercaptan, among others.These may be used either singly or in the form of a mixture of two ormore.

The radical polymerization initiator may be any of known oil-soluble andwater-soluble polymerization initiators. For efficient production ofpolymers having a terminal alkylthio group, said initiator shouldpreferably be used in an amount of 1 mole or less, more preferably notmore than 0.1 mole, per mole of the alkylmercaptan [B].

Depending on their properties, the polymers [IIa] and [IIb] can beproduced by any of the bulk polymerization, solution polymerization andsuspension polymerization methods. A polymerization temperature of50°-150° C. and a polymerization period of 1-8 hours are preferred. Thesolvent for solution polymerization may be any solvent provided that thepolymerizable monomer composition [A], alkylmercaptan [B] and radicalpolymerization initiator are soluble in it and that it will notinterfere with the radical polymerization.

The polymerizable monomer or monomers (c) to be used in the synthesis ofthe polymer [IIb] are now described in further detail. Thesepolymerizable monomers (c) contain a group reactive with a carboxylgroup and in addition a polymerizable unsaturated group. They are usedfor the purpose of introducing a polymerizable unsaturated group intothe polymer to be used as the emulsifier. As examples of suchpolymerizable monomers (c), there may be mentioned epoxy groupcontainingpolymerizable monomers, such as glycidyl (meth)acrylate and (meth)allylglycidyl ether; oxazoline group-containing polymerizable monomers, suchas 2-isopropenyl-2-oxazoline and 2-vinyl-2-oxazoline; aziridinegroup-containing polymerizable monomers, such as 2-aziridinylethyl(meth)acrylate and (meth)acryloylaziridine; and hydroxylgroup-containing polymerizable monomers, such as 2-hydroxyethyl(meth)acrylate, (meth)allyl alcohol, and monomer esters between(meth)acrylic acid and polypropylene glycol or polyethylene glycol.These may be used either singly or in the form of a mixture of two ormore.

In this case, the amount of the polymerizable monomers (c) should besuch that they will not consume the free carboxyl group contained in thepolymerizable monomer composition [A] to an excessive extent as a resultof their reaction with said carboxyl group or in other words, such thatthe acid value of the emulsifier can be retained at a level not lessthan 200.

The polymers [IIb] and/or salts thereof as synthesized by using thepolymerizable monomers (c) are polymerizable. When such polymers areused as the emulsifiers in emulsion-polymerizing the monomer composition[I], the copolymerization reaction of said polymers [IIb] and/or saltsthereof and the monomer composition takes place in addition to thecrosslinking reaction between the carboxyl group which said polymers[IIb] and/or salts thereof have and the functional group contained insaid monomer composition [I] and reactive with the carboxyl group,whereby the integration is more promoted as compared with the case wherethe polymers [IIa] and/or salts thereof are used. Furthermore, the useof the polymers [IIb] and/or salts thereof allows the reaction of thedouble bond of the polymerizable monomer (a) and/or the polymerizablemonomer (b) of the monomer composition [I] with the double bond of theemulsifier in the manner of grafting already in the state of aqueousdisperison before film formation. As a result, the foaming of theaqueous crosslinkable resin dispersion is advantageously more decreased.Therefore, as compared with the case where the polymers [IIa] and/orsalts thereof are used, the aqueous crosslinkable resin dispersionsobtained with the polymers [IIb] and/or salts thereof the integration ofwhich with the polymer formed by emulsion polymerization can be readilypromoted can exhibit much improved performance characteristics invarious fields of application.

The polymerizable monomers (c) are preferably used in an amount of 1-100molecules, more preferably 1-10 molecules, per molecule of the polymer[IIb]. When the polymerizable monomer composition [A] contains ahydroxyl group-containing polymerizable monomer, the polymerizablemonomer or monomers (c) should preferably contains an epoxy, oxazolineor aziridine group.

In synthesizing the polymers [IIb], the polymers [IIa] as they arereacted with the polymerizable monomers (c), if necessary after dilutionwith a solvent. In that case, the reaction is preferably carried out atordinary temperature to 200° C., more preferably 50°-150° C. Thepolymers [IIa] and [IIb] preferably have a molecular weight 400-10,000,more preferably 400-5,000.

In accordance with the present invention, the above-mentioned polymers[IIa] and/or [IIb], and/or salts thereof (sometimes referred to also aspolymer salts) are used as the emulsifiers.

The above-mentioned polymer salts can be obtained by neutralizing inadvance part or the whole of the polymerizable monomer or monomers (a)to be used in the production of the polymers [IIa] with a basic compoundand then performing the polymerization by the same procedure as used inproducing the polymers [IIa] and/or [IIb]. Alternatively, they can beobtained by adding a basic compound to the polymers [IIa] and/or [IIb].In this case, the basic compound is added in an amount sufficient toneutralize part or the whole of the carboxyl group in the polymers.

Although the polymers [IIa] and [IIb] are already surface-active, theiruse in the form of a salt resulting from partial or entireneutralization of the carboxyl group can lead to improved dispersionstability of the polymer particles formed and this makes it possible toobtain aqueous crosslinkable resin dispersions excellent in stabilityduring emulsion polymerization and during storage. In this case, it ispreferable, however, to neutralize the carboxyl group only partially,since complete neutralization of the carboxyl group may lead todecreased crosslinkability of the polymer formed by emulsionpolymerization and the emulsifier.

Usable as the neutralizing agent are bases in general use, for examplealkali metal compounds, such as sodium hydroxide and potassiumhydroxide; alkaline earth metal compounds, such as calcium hydroxide andcalcium carbonate; ammonia; and water-soluble organic amines, such asmonomethylamine, dimethylamine, trimethylamine, monoethylamine,diethylamine, triethylamine, monopropylamine, dimethylpropylamine,monoethanolamine, diethanolamine, triethanolamine, ethylenediamine anddiethylenetriamine. These may be used either singly or in the form of amixture of two or more. When more improved coat film water resistance isdesired, low-boiling temperature amines capable of evaporating at anordinary temperatures or upon heating, for example ammonia,monomethylamine, dimethylamine, trimethylamine and the like, arepreferably used.

The polymers [IIa] and/or salts thereof, which belong to the group (P),and the polymers [IIb] and/or salts thereof, which belong to the group(Q), as obtained by the above process can produce remarkable effects asthe emulsifiers in the practice of the invention. For securing theemulsion stability during processing of the aqueous crosslinkable resindispersions, and at the same time for making the characteristic effectsof the present invention to be produced more fully, in variousapplications, said emulsifiers should preferably satisfy the followingrequirements from the structural formula viewpoint:

That they should have R₁ S-- [R₁ being alkyl having 6 to 18 carbonatoms] at one end of their molecule and --H at the other and compriserepeating units of the general formulas ##STR3## in which R₂ to R₈ arethe same or different in and/or among the units T, U, V and W and eachis hydrogen, halogen, methyl, carboxyl, alkoxycarbonyl or COO⁻⁻.M⁺ [M⁺being ammonium cation, amine cation, alkali metal cation or half ofalkaline earth metal cation], X⁺ is always the same or may differ fromone occurrence to another occurrence of the unit U and stands forammonium cation, amine cation, alkali metal cation or half of alkalineearth metal cation, Y is a group having a polymerizable unsaturatedbond, Z is nitrile (cyano), phenyl, substituted phenyl, amido(carbamoyl), N-mono- or N,N-disubstituted amido, alkoxycarbonyl or agroup of the formula COO--R₉ --O)_(n) H [R₉ being alkylene having 2 to 4carbon atoms and n being an integer of 1 to 50], said repeating units T,U, V and W being arranged in an optional order provided that thefollowing numerical conditions should be satisfied: that the number ofoccurrences of T and the number of occurrences of U are eachindependently 0 or 1 to 500, with a total number of occurrences of T andU of 1 to 500, that the number of occurrences of V is 0 or 1 to 100 andthat the number of occurrences of W is 0 or 1 to 250.

The meaning of each symbol used above is explained hereinbelow.

First, the alkyl having 6 to 18 carbon atoms, which is represented by R₁includes, among others, such straight or branched alkyls as hexyl,heptyl, octyl, nonyl, decanyl, undecanyl, dodecanyl, tetradecanyl,pentadecanyl, octadecanyl, 2,3,5-trimethylhexanyl,2,7,8-trimethyldecanyl and 5-methyl-4-propyldecanyl.

Referring to R₂ to R₈, the halogen represented thereby includesfluorine, chlorine, bromine and iodine, the alkoxycarbonyl representedthereby includes, among others, methoxycarbonyl, ethoxycarboyl,propoxycarbonyl, isopropoxycarbonyl, butyloxycarbonyl,tertbutyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl,2-ethylhexyloxycarbonyl, dodecanyloxycarbonyl andoctadecanyloxycarbonyl.

Examples of the amine cation represented by M⁺ or X⁺ aredimethylammonium, diethanolammonium, trimethylammonium,triethylammonium, pyridinium and picolinium; examples of the alkalimetal cation represented thereby are sodium ion and potassium ion; andexamples of the alkaline earth metal ion are magnesium ion, calcium ionand barium ion.

Among the groups represented by Z, the substituted phenyl is, forexample, tolyl, α-methylnaphthyl, β-methylnaphthyl, hydroxyphenyl,aminophenyl, nitrophenyl or cyanophenyl.

Among the groups represented by Z, the substituent for the hydrogen atomof the amido group may have includes, among others, alkyls such asmethyl, ethyl, propyl, isopropyl, butyl, tert-butyl and hexyl, andhydroxyalkyls such as methylol, hydroxyethyl, hydroxypropyl,hydroxyisopropyl, and the like.

Among the groups represented by Z, the alkoxycarbonyl may include thoseexamples given hereinabove.

As the alkylene of 2 to 4 carbon atoms as represented by R₉ there may bementioned ethylene, propylene, butylene and 2-methylpropylene, amongothers.

The above examples are all typical examples in the practice of thepresent invention and it is to be noted that the scope of the presentinvention is by no means limited to such examples.

The total sum of occurrences of the above-mentioned T, U, V and W ispreferably 2 to 150, more preferably 2 to 70, in each emulsifiermolecule.

The aqueous crosslinkable resin dispersion according to the inventioncan be produced by emulsionpolymerizing in an aqueous medium a monomercomposition [I] composed of 0.1-40% by weight of at least onepolymerizable monomer (a) having, within its molecule, a group reactivewith a carboxyl group and 60-99.9% by weight of one or more otherpolymerizable monomers (b) [the sum total of the polymerizable monomers(a) and (b) being 100% by weight] in the presence of a water-soluble orwater-dispersible emulsifier or emulsifiers selected optionally from oneor both of the group (P), which includes the above-mentioned polymers[IIa] and/or salts thereof, and the group (Q), which includes thepolymers [IIb] and/or salts thereof.

The polymerizable monomer (a) is a compound having, within its molecule,a polymerizable double bond and in addition a group reactive with acarboxyl group, such as an epoxy, aziridine or oxazoline group. Asexamples of this polymerizable monomer (a), there may be mentioned thoseexamples given above referring to the polymerizable monomers (c) whichare used in synthesizing the polymerizable unsaturated group-containingpolymers [IIb]. Among them, however, those polymerizable monomers whichcontain an epoxy, oxazoline or aziridine group are preferably used.

The polymerizable monomer (a) is used for the purpose of introducing agroup reactive with a carboxyl group into the polymer formed by emulsionpolymerization. By this it becomes possible for the above-mentionedpolymer and the emulsifier to react with each other to form a covalentbond. Said monomer (a) is used in an amount of 0.1-40% by weight, morepreferably 0.5-20% by weight, of the monomer composition [I]. If theamount of the polymerizable monomer (a) is less than 0.1% by weight,films obtained from the aqueous crosslinkable resin dispersion will havean insufficient crosslinking density, hence the desired improvements inwater resistance, solvent resistance and durability will not be producedto a satisfactory extent. When, conversely, said monomer (a) is used inan amount exceeding 40% by weight, the product films will become hardand brittle. In either case, the utility of said dispersion will bedecreased in various fields of application.

The other polymerizable monomer (b) is not limited to any particularspecies or class but may be any monomer provided that it iscopolymerizable with the polymerizable monomer (a). Said monomer (b)thus includes, among others, styrene and styrene derivatives, such asvinyltoluene, α-methylstyrene, chloromethylstyrene, styrenesulfonic acidand salts thereof; (meth)acrylamide and derivatives thereof, such asN-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide andN,N-dimethyl(meth)acrylamide; (meth)acrylic acid esters synthesized byesterification of (meth)acrylic acid with C₁ -C₁₈ alcohols, such asmethyl (meth)-acrylate, ethyl (meth)acrylate and butyl (meth)acrylate;2-sulfoethyl (meth)acrylate and salts thereof, vinylsulfonic acid andsalts thereof, vinyl acetate, (meth)acrylonitrile; polymerizable basicmonomers, such as dimethylaminoethyl (meth)acrylate,dimethylaminoethyl(meth)acrylamide, dimethylaminopropyl(meth)acrylamide,vinylpyridine, vinylimidazole and vinylpyrrolidone; polyfunctional(meth)acrylic acid esters having two or more polymerizable unsaturatedgroups within their molecule, for example esters of (meth)acrylic acidwith polyhydric alcohols such as ethylene glycol, 1,3-butylene glycol,diethylene glycol, 1,6-hexane glycol, neopentyl glycol, polyethyleneglycol, polypropylene glycol, trimethylolpropane, pentaerythritol anddipentaerythritol; (meth)acrylamides, such as N-methylol(meth)acrylamideand N-butoxymethyl(meth)acrylamide; organic silicon-containing monomers,such as vinyltrimethoxysilane,γ-(meth)acryloyloxypropyltrimethoxysilane, allyltriethoxysilane,trimethoxysilylpropylallylamine, vinyltriethoxysilane,vinyltrimethoxyethoxysilane, (meth)acryloyloxypropyltriethoxysilane and(meth)acryloyloxypropylmethyldimethoxysilane; vinyl fluoride, vinylidenefluoride, vinyl chloride, vinylidene chloride, divinylbenzene anddiallyl phthalate.

In a preferred embodiment of the invention, an organicsilicon-containing monomer is used among the other polymerizablemonomers (b). Organic silicon-containing monomers are compounds having,within their molecule, a polymerizable unsaturated group and ahydrolyzable group directly bound to the silicon atom and are effectivein improving the adhesion to various kinds of substance, thus making itpossible to provide aqueous crosslinkable resin dispersions more usefulin various fields of use. The use of an organic silicon-containingmonomer in an amount of 0.1-20% by weight based on the monomercomposition [I] will give favorable results.

The aqueous crosslinkable resin dispersion according to the inventioncan be produced by any of the so-far known emulsion polymerizationprocesses. Thus, for instance, the technique comprising subjecting topolymerization the whole mixture of a polymerization catalyst, water,the above-mentioned emulsifier, and the monomer composition [I], or theso-called monomer dropping method, pre-emulsion method, seedpolymerization method or multistep polymerization method can beemployed.

In a more preferred embodiment of the invention, the multisteppolymerization method is used. Thus, the monomer composition [I] isdivided into two or more portions differing in composition from eachother [e.g. differing in the content of polymerizable monomer (a)] andmultistep polymerization is carried out by feeding these portionssuccessively, whereby the storage stability and crosslinkability of theaqueous crosslinkable linkable resin dispersion can be both improvedsimultaneously. According to a technique of multistep polymerization bywhich this effect can be produced most efficiently, a monomer portionwhich does not contain any polymerizable monomer (a) is subjected topolymerization in the last step.

The emulsion polymerization is carried out generally at a temperature of0°-100° C., preferably 50°-80° C., for a period of 1-10 hours. Inperforming emulsion polymerization, a hydrophilic solvent, a knownemulsifier and other additives may be added if, at the addition levelsemployed, they will not adversely affect the physical properties of thecoat films.

The amount of the emulsifier or emulsifiers selected from one or both ofthe groups (P) and (Q) is not critical. Preferably, however, they areused in an amount of 0.5-20 parts by weight, more preferably 1-15 partsby weight, per 100 parts by weight of the polymerizable monomer mixture.

The polymerization catalyst may be any of the so-far known ones. Forproducing aqueous resin dispersions capable of giving coat films moreexcellent in water resistance, however, polymerization catalysts whichwill not leave the sulfate ion, such as hydrogen peroxide, di-t-butylperoxide, peracetic acid, 2,2'-azobis(2-amidinopropane) dihydrochlorideand 4,4'-azobis(4-cyanopentanoic acid), should preferably be used eithersingly or in the form of a mixture of two or more. In cases where atleast one of the polymerizable monomers has a functional group reactivewith a carboxyl group, 2,2'-azobis(2-amidinopropane) dihydrochloride,4,4'-azobis(4-cyanopentanoic acid) and the like, which have, withintheir molecule, an amidino, carboxyl or the like group highly reactivewith the above-mentioned reactive group, are more preferred. Generally,the polymerization catalyst is used in an amount of 0.01-5 parts byweight per 100 parts by weight of the polymerizable monomer composition.

As mentioned above, the aqueous crosslinkable resin dispersion isobtained by emulsion-polymerizing a monomer composition comprising, asan essential component thereof, a polymerizable monomer having a groupreactive with a carboxyl group using as the emulsifier a polymer havinga side-chain carboxyl group and a terminal long-chain alkyl thio groupand/or a salt thereof. Therefore, the polymer formed by emulsionpolymerization and the emulsifier can be bound to each other to form acrosslinked product. The polymers and their salts belonging to thegroups (P) and (Q), which are used in accordance with the invention,serve as emulsifiers in the step of emulsion polymerization, enablingformation of a stable emulsion, and, in the step of film formation as aresult of evapoaration of water, they behave as crosslinking agents,serving to convert the films to three-dimensionally crosslinked ones.The crosslinking reaction can proceed smoothly even at room temperatureand can proceed more smoothly under heating. Heating at 60°-130° C. isgenerally sufficient. Such high temperatures exceeding 150° C. as in thecase of crosslinking of known melamine resins are not necessary. Theaqueous crosslinkable resin dispersion according to the invention canform films excellent in water resistance, solvent resistance,durability, heat resistance and adhesion, since, as mentioned above, thepolymer formed by emulsion polymerization can integrate with theemulsifier to form a crosslinked product without leavinglow-molecular-weight hydrophilic emulsifier residues in the films.

The aqueous crosslinkable resin dispersion per se is thus excellent inperformance and can be used as a coating composition, adhesive,textile-finishing composition and so forth. It is possible to producefurther improvements in adhesion and heat resistance and/or giveantistatic property to thereby increase the utility of said dispersionby adding a metal oxide and/or metal hydroxide in the form of fineparticles (hereinafter, fine-particle material) thereto to give anaqueous composition. The fine-particle material to be used here is afine-particle hydroxide or oxide containing one or more metalsrepresented by the chemical symbols of elements Si, Ti, Al, Sb, Zr, Ce,V, Nb, Ga, In, Fe, Mn, Ni, Co, Ta, Sn, Mg and W, and the particle sizeof single particles is within the range of 1 to 1,000 nm. Said singleparticles may be either primary particles or their aggregates, namelysecondary particles, and the fine-particle material can be used in theform of a powder or in the state of a sol dispersed in water and/or anorganic solvent for example a hydrosol or organosol. The fine-particlematerial may consist of a single metal hydroxide or oxide or a compoundhydroxide or oxide containing two or more metal species. In particular,aqueous colloidal silica is most preferred since it is well compatiblewith the aqueous crosslinkable resin dispersion, excellent inperformance and readily available.

Aqueous colloidal silica is silicic acid condensate. Its particle sizeis preferably within the range of 5-100 mμ, in particular 7-50 mμ. Thosecommercial products which are usually supplied in the form of aqueousdispersions can be used as they are. As such aqueous colloidal silicaproducts, there may be mentioned such commercial products as "SnowtexO", "Snowtex N", "Snowtex NCS", "Snowtex 20" and "Snowtex C" (all beingproducts of Nissan Chemical Industries), "Cataloid SN" and "CataloidSi-500" (both being products of Catalysts and Chemicals Industries) aswell as surface-treated colloidal silica, for example aluminicacid-treated "Cataloid SA" (product of Catalysts and ChemicalsIndustries). One or more selected from among these can be used.

The fine-particle material is used in an amount of 1-200 parts by weightper 100 parts by weight (on the solids basis) of the aqueouscrosslinkable resin dispersion. When said material is used in an amountoutside of the above range, no effects will be produced or the balanceamong performance characteristics will be disadvantageously disturbed.In cases where a fine-particle material is used in combination, it isparticularly preferable that the aqueous crosslinkable resin dispersionbe one produced using an organic silicon-containing monomer. Since ahydrolyzable group involving silicon as derived from the organicsilicon-containing monomer is introduced into the polymer and improvedthe compatibility between the polymer and the fine-particle material,the fine-particle material and the polymer can form a more closely andintimately bound composite material and, as a result, the characteristicfeatures of the aqueous composition according to the invention can beenjoyed more fully. Said aqueous composition can be prepared by merelymixing the aqueous crosslinkable resin dispersion with a fine-particlematerial, if necessary with heating, or by producing the aqueouscrosslinkable resin dispersion in the presence of a fine-particlematerial.

The mucosity, wetting of various base materials or substrates,adhesiveness and other properties can be more improved and the utilityin various fields of application can be increased when an aqueous resincomposition is derived from the aqueous crosslinkable resin dispersionby adding thereto a water-soluble resin. The water-soluble resin to beused here includes water-soluble resins selected from among starch,cellulose, casein, polyvinyl alcohol, polyester compounds, polyethercompounds, polyamide compounds, polyamine compounds, and water-solublederivatives of these. Particularly preferred among them is polyvinylalcohol. Polyvinyl alcohol can interact with the aqueous crosslinkableresin dispersion according to the invention in a unique manner,adjusting the viscosity of said dispersion in a favorable manner andeffectively and greatly improving the stability, ability to wet varioussubstances, and adhesion thereto of said dispersion as well as the filmstrength. Various polyvinyl alcohol species differing in degree ofpolymerization and degree of saponification over a wide range can beused effectively. Preferably, however, the polyvinyl alcohol species tobe used in accordance with the invention should have a degree ofpolymerization of 200-3,500 and a degree of saponification of 70-100mole percent.

The water-soluble resin is used preferably in an amount of 0.001-100parts by weight, more preferably 0.01-50 parts by weight, per 100 partsby weight (on the solids basis) of the aqueous crosslinkable resindispersion. If the water-soluble resin is used in an amount below 0.001part by weight, the effects of addition thereof will be insignificant,whereas, in amounts exceeding 100 parts by weight, the excellentperformance characteristics of the aqueous crosslinkable resindispersion may not be enjoyable to the full.

The aqueous resin composition can be produced, for example by thefollowing methods (1) to (3): (1) Mixing the aqueous crosslinkable resindispersion with a water-soluble resin; (2) Preparing the aqueouscrosslinkable resin dispersion by emulsion-polymerizing thecorresponding polymerizable monomers in the presence of a water-solubleresin; and (3) Treating the aqueous crosslinkable resin dispersion and awater-soluble resin in the presence of a radical polymerizationcatalyst. For the purpose of improving the water resistance of theaqueous resin composition, the methods (2) and (3) are preferred.Preferred as the radical polymerization catalyst to be used in emulsionpolymerization in carrying out the method (2) and as the radicalpolymerization catalyst to be used in carrying out the method (3) arethose possibly capable of causing a hydrogen abstraction reaction, forexample peroxides such as hydrogen peroxide, di-t-butyl peroxide,peracetic acid and persulfates.

A water-dispersible composition obtained by adding 1-200 parts by weightof a metal oxide and/or metal hydroxide in the form of fine particlesand 0.001-100 parts by weight of a water-soluble resin to 100 parts byweight (on the solids basis) of the aqueous crosslinkable resindispersion has the characteristic features of the above-mentionedaqueous composition and those of the aqueous resin compositioncombinedly and can exhibit its performance characteristics effectivelywhen used in various applications such as mentioned below.

The aqueous crosslinkable resin dispersion, aqueous composition, aqueousresin composition and water-dispersible composition according to thepresent invention (hereinafter also referred to as "aqueous dispersionand other compositions" or the like), as they are, can be used ascoating compositions. If necessary, they may further contain knownadditives or the like, such as pigments, fillers, thickeners, pHadjusting agents, ultraviolet absorbers, crosslinking agents, filmformation auxiliaries, penetrants, wetting agents and antistatic agents,each in an appropriate amount.

The coating compositions according to the invention have advantageouscharacteristic features. They are excellent in adhesiveness to varioussubstrates, water resistance, moisture resistance and durability, freefrom the risk of fire or environmental pollution because of their beingaqueous dispersions or the like, and less subject to foaming and easierto handle as compared with aqueous resin dispersions or the likeproduced by using known low-molecular-weight emulsifiers. Therefore, thecoating compositions according to the invention can be utilized veryeffectively as coating compositions for metals, wood, inorganic buildingmaterials, plastics, paper, and so forth. When, for instance, they areused as coating compositions for metal substrates, such as stainlesssteel sheets, galvanized sheets aluminum sheets, or woody substrates,such as plywoods, wood floorings and woody wall materials, coatingsexcellent in appearance, adhesion, water resistance and durability canbe obtained. In a most preferred example, where the coating compositionsaccording to the invention are applied to inorganic substrates, saidcompositions can exhibit their characteristic features to the fullestextent. The coating compositions according to the invention areexcellent in adhesion to various inorganic building materials and inwater resistance, hence the films formed therefrom will not swell orpeel off even when moistened with water. They can also avoid whitecoating formation, which is a problem encountered with cement-basedbuilding materials. Thus, a beautiful appearance can be maintained for aprolonged period. Furthermore, when they are used as coatingcompositions for exterior building materials, the deterioration inphysical properties will be minimum owing to their excellent durabilitycharacteristics. Therefore, when applied to floors, walls or ceilingsfinished with cement, mortar and concrete or to gypsum boards, asbestosslates, asbestos boards, precast concrete substrates, light-weightaerated concrete substrates, fiber-reinforced concrete substrates, thickslates, asbestos cement-calcium silicate plates, glass sheets, tiles,bricks, fired roofings, and other inorganic building materials, saidcompositions can serve as coating compositions or primers intended, forinstance, to protect substrates, provide beautiful appearance, givewater resistance and protect against dust, and can exhibit theirexcellent performance characteristics.

The coating compositions according to the invention are particularlyeffective in coating plastics as well. For example, they show goodadhesiveness to substrates made of various general-purpose plastics andengineering plastics, inclusive of plastics resistant to adhesion, suchas polyethylene terephthalate, and the coat films obtained therefrom areexcellent in performance characteristics such as water resistance, hotwater resistance, durability and antistatic property. Therefore, thecoating compositions according to the invention are useful as primersfor polyethylene terephthalate film printing, aluminum vapor depositionand magnetic coating, and as vehicles for antistatic treatment andsurface-roughening coating. They can also be used effectively as coatingcompositions for ornamentation, protection and/or functionalization ofmoldings and sheet films made of ABS, polyolefins, polycarbonates,acrylic resins, polybutylene terephthalate and other synthetic resins.When applied to polyester films, among others, they can produce markedeffects, providing polyester films excellent in affinity for orcompatibility with various printing inks, metal vapor deposited films,magnetic coatings and so forth. In applying the coating compositionsaccording to the invention to polyester films, it is particularlysuitable to use said compositions in the form of aqueous resincompositions composed of the aqueous crosslinkable resin dispersion andpolyvinyl alcohol. When said aqueous resin compositions are used ascoating compositions, polyester films are wet well with them and smoothand uniform coating layers can be formed. For the production ofpolyester films having a coat layer having a minimum required thicknessto protect the substrates, namely polyester films, against dust andallow the desired performance characteristics to be exhibited by usingthe coating compositions according to the invention, it is effective toproduce them by a method (in-line coating process) which comprisesapplying the coating compositions to melt-extruded polyester films notyet fully stretched to a desired extent and then completing thestretching. The polyester films not yet fully stretched include, amongothers, unstretched films, uniaxially stretched films (films stretchedin one direction only) and low ratio stretched films stretched only to astretching ratio lower than the desired one. A production method whichis particularly preferred from the economy and coating layer qualityviewpoints comprises stretching melt-extruded polyester resin sheets orfilms in the longitudinal direction to a desired stretching ratio,applying the coating compositions according to the invention to thesame, then stretching the same in the lateral direction to a desiredratio, and fixing the same thermally.

The coating compositions according to the invention are also useful inpaper coating. The coating compositions have good affinity for variousinorganic fillers conventionally used in paper coating compositions andfor inorganic porous particles and others used in the ink-absorbinglayer of ink jet recording paper sheets and at the same time givecoatings having good water resistance and, therefore, are useful asbinders in various paper coating compositions. They are also suited foruse as over coat compositions, under coat compositions, back coatcompositions and so forth in the manufacture of pressure-sensitiverecording paper and heat-sensitive recording paper, where the excellentwater resistance and heat resistance can be utilized efficiently.

The coating compositions according to the invention, when applied, asover coat compositions, onto the heat-sensitive color-developing layerof heat-sensitive recording paper, can provide very excellentperformance characteristics. For their use as over coat compositions,the over coat compositions are prepared by adding a crosslinking agentand a filler to the aqueous crosslinkable resin dispersion obtained byemulsion-polymerizing the monomer composition [I] which contains anorganic silicon-containing monomer. In that case, further addition ofpolyvinyl alcohol gives over coat compositions which can giveheat-sensitive recording paper excellent in smoothness. Furthermore, theuse of over coat compositions supplemented with colloidal silicapreferably gives heat-sensitive recording paper more improved in heatresistance. As the above-mentioned crosslinking agent, those that canreact at temperatures as low as possible are preferred and, for example,methylolurea, methylolmelamine, methylolguanamine and the likepolymethylol compounds; glyoxal, glutaraldehyde, dialdehyde starch andthe like polyaldehyde compounds; polyethylene glycol diglycidyl ether,glycerol diglycidyl ether, trimethylolpropane diglycidyl ether and thelike nonionic water-soluble epoxy compounds; water-soluble copolymers ofacrylic or methacrylic acid glycidyl ester and acrylamide or the like;polyamide epoxy resins; boric acid, borates; zirconium compounds of thechemical formulas Na₂ ZrSiO₂, ZrOCa₂. 3H₂ O, ZrOSO₄.nH₂ O, ZrO(NO₃)₂ 4H₂O, ZrO(CO₃)₂.nH₂ O, ZrO(OH)₂.nH₂ O, ZrO(C₂ H₂ O)₂, (NH₄)₂ ZrO(CO₃)₂ andZrSiO₄ ; and others can be used. As the filler mentioned above, theremay be mentioned, for example, inorganic fine-particle materials, suchas calcium carbonate, silica, zinc oxide, titanium oxide, aluminumhydroxide, zinc hydroxide, barium sulfate, clay, talc, andsurface-treated calcium or silica, as well as organic fine-particlematerials, such as urea-formalin resins, styrene-methacrylic acidcopolymers and polystyrene resins. Heat-sensitive recording paper havingimproved water resistance and solvent resistance, good storability andhigh glossiness can be obtained by forming such an overcoat layer on theheat-sensitive color-developing layer. In this case, the use, as thesupport member, of polyolefin-based resin synthetic paper produced bythe film method is preferable, since said synthetic paper is superior instrength, smoothness and water resistance to paper species obtained fromnature-derived cellulose fibers, for instance. When such film-methodpolyolefin-based resin synthetic paper is used, coating compositionssupplemented with polyvinyl alcohol are used as the over coatcompositions. The film-method polyolefin-based resin synthetic papermentioned above include monolayer structure films obtained by admixing afiller and additives (stabilizer, dispersant, etc.) with apolyolefin-based resin, melting and kneading the compound in anextruder, extruding the melt through a die slit and subjecting theextrudate to simultaneous or successive biaxial stretching, as well asmultilayer structure films comprising a substrate layer, a paper-likelayer and optionally a surface layer.

The aqueous dispersions and other compositions according to theinvention are useful as textile finishing compositions. Since they areexcellent in adhesiveness to natural or synthetic, organic or inorganicfibers, they can be used as binders for nonwoven fabrics and paper madeof such fibers and as surface treating compositions, adhesives and othercompositions to be applied to cloths, paper and other textile productsmade of said fibers.

When organic fibers, such as cotton, wool, acrylic fibers, polyesterfibers, nylon fibers and rayon fibers, are the targets of application,they can be used as binders for various nonwoven fabrics for clothing orindustrial use, binders for use in textile printing, binders for use inflocking, back coat compositions for carpets, coating compositions forcoated fabrics having a coat layer provided for the purpose of modifyingthe feeling and/or waterproofing, and adhesives for manufacturingcloth-cloth or clothfilm bonded fabrics, among others, to give productsor articles excellent in water resistance, washability and durability.They can be used safely in products to be used as articles of clothingsince they will not generate formalin in the heating treatment step orsteps in the course of their processing. When the targets of applicationare inorganic fibers, they are useful as binders for bundling orcollecting inorganic fibers, such as glass fibers, mineral fibers andceramic fibers, and as binders for use in the manufacture of nonwovenfabrics, paper, waddings and others from such fibers. Thus, forinstance, they can be effectively used as binders in the manufacture ofwet or dry method glass fiber mats useful as reinforcements for printedcircuit substrates, separators for use in less storage batteries, etc.;wet or dry method glass paper or ceramic paper species useful as airfilters, etc.; chopped strands, robings or yarns made of inorganicfibers and useful as reinforcements for various composite materials;rock wool or glass wool useful as a thermal insulator; and otherinorganic fiber nonwoven fabrics or woven fabrics, or inorganic fiberbundles.

The aqueous dispersions and other compositions according to the presentinvention may be used, as they are, as textile finishing compositions.If necessary, however, known additives or auxiliaries, such as pHadjusting agents, viscosity control agents, coupling agents, lubricants,antistatic agents, water-repellents, crosslinking agents, ultravioletabsorbers, penetrants, pigments and dyes, may be added. Saidcompositions may be used after an adequate dilution.

The aqueous dispersions and other compositions according to theinvention are useful as adhesives. Since they have good adhesiveness tovarious substrates, they are suited for use as adhesives for metals,wood, paper, films, inorganic materials, etc. In particular, when thepolymer obtained by polymerizing the monomer composition [I] has a glasstransition temperature within the range of -80° to 0° C., preferably-70° to -30° C., the compositions are effective as pressure-sensitiveadhesives.

The pressure-sensitive adhesives in which the aqueous dispersions andother compositions according to the invention are used are excellent notonly in adhesion in the dry state but also in water resistance andmoisture resistance. Therefore the adhesive layer will not undergowhitening or blushing even when immersed in water. Furthermore, evenunder high humidity conditions, the adhesion and creep resistance willnot be decreased. Therefore, said adhesives can be applied in thosefields in which high performance characteristics are required, where theconventional adhesives cannot be used. In addition, excellent adhesioncan be achieved with them even at low temperatures and repeelability canbe provided with them, they can be used in various fields where thesecharacteristics are demanded. Thus, they are very useful as adhesivesfor paper-, cloth- or plastic-based adhesive labels, adhesive tapes, andadhesive sheets.

The aqueous dispersions and other compositions according to theinvention can be used, as they are, as adhesives. If necessary, however,known additives or auxiliaries, such as pH adjusting agents, viscositycontrol agents, crosslinking agents, tackifiers, wetting agents,lubricants, ultraviolet absorbers and film-forming auxiliaries, may beadded thereto.

In uniting bodies by using the aqueous dispersions and othercompositions according to the invention as adhesives, any method can beused without any particular limitation. As one effective means ofincreasing the bond strength, there may be mentioned heating of thebody-body assemblies bonded by the intermediary of the adhesives to atemperature above the glass transition temperature of the aqueouscrosslinkable resin.

The aqueous dispersions and other compositions according to theinvention are useful as binder components of coating compositions forheat-sensitive color-developing layer formation. So far, water-solubleresins, such as polyvinyl alcohol, have been used as binder componentsof coating compositions for heat-sensitive color-developing layerformation. However, they can give only poor water resistance and,therefore, when the image-developed (i.e. thermally recorded) sidebecomes wet with water, the characters and figures may partly or whollydisappear or become unreadable disadvantageously. On the contrary, thisdrawback can be overcome and heat-sensitive recording media having goodwater resistance can be obtained by using the aqueous dispersions andother compositions according to the present invention. While the supportmember for heat-sensitive recording media may be optional, the use ofpaper is advantageous from the price and application range viewpoints.For obtaining transparent heat-sensitive recording media, the use ofpolyester films and the like plastic films is recommendable. When apressure-sensitive color developing system is used in lieu of theheat-sensitive color-developing system, pressure-sensitive recordingmedia, also of high quality, can be obtained. In this mode ofapplication, other known additive or additives can optionally be used inaddition to the aqueous dispersions and other compositions according tothe invention and the heat- or pressure-sensitive color-developingcomponents.

The following examples are given for the purpose of illustrating thepresent invention and they should not be used for limiting the scope ofthe invention. In the following, "part(s)" and "%" are "part(s) byweight" and "% by weight", respectively.

EXAMPLE 1 Emulsifier Production

A flask equipped with a dropping funnel, stirrer, nitrogen inlet tube,thermometer and reflux condenser was charged with 180 parts of isopropylalcohol, and the contents were heated to 80° C. while nitrogen gas wasblown into the flask gently. Then, thereto was added dropwise over 1.5hours a polymerizable monomer mixture composed of 174 parts of acrylicacid, 36 parts of n-dodecylmercaptan and 0.42 part of2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN). Duringthe dropping, the temperature was maintained at 80°-85° C. and, aftercompletion of the dropping, the resultant mixture was stirred at thesame temperature for 1 hour for driving the polymerization tocompletion. To the thus-obtained polymer composition were further added57 parts of allyl glycidyl ether and 21 parts of triethylbenzylammoniumchloride, the resultant mixture was heated to 85° C., and the reactionwas conducted at the same temperature for 6 hours to give a 57% solutionof emulsifier E-1. Acid value measurement confirmed that the reactionhad been completed. The number average molecular weight of emulsifierE-1 was 1,500 and the acid value thereof was about 400.

EXAMPLE 2 Emulsifier Production

The same flask as used in Example 1 was charged with 180 parts ofisopropyl alcohol, which was then heated to 80° C. under nitrogen.Thereto was added dropwise over 2.0 hours a polymerizable monomermixture composed of 148 parts of acrylic acid, 31 parts of itaconicacid, 18 parts of 2-ethylhexyl acrylate, 24 parts of n-octylmercaptanand 0.41 part of AIBN. After completion of the dropping, the resultantmixture was stirred under reflux for 1 hour for driving thepolymerization to completion. To the thus-obtained polymer was added 77parts of 2-aziridinylethyl methacrylate, and the mixture was refluxedfor 4 hours to give a 62% solution of emulsifier E-2. The number averagemolecular weight of said emulsifier E-2 was 1,800 and the acid valuethereof was about 380.

EXAMPLE 3 Emulsifier Production

The same flask as used in Example 1 was charged with 180 parts ofisopropyl alcohol, which was then heated to 80° C. under nitrogen.Subsequently, a polymerizable monomer mixture prepared in advance andcomposed of 125 parts of acrylic acid, 100 parts of 2-hydroxyethylacrylate, 36 parts of n-dedecylmercaptan, 30 parts of isopropyl alcoholand 0.30 part of AIBN was added dropwise over 1 hour for effectingpolymerization. After completion of the dropping, the mixture wasmatured under reflux for 1 hour for driving the polymerization tocompletion. To the thus-obtained polymer was further added 56 parts of2-isopropenyl-2-oxazoline, and the mixture was refluxed for 6 hours togive a 60% solution of emulsifier E-3. The number average molecularweight of said emulsifier E-3 was 1,800 and the acid value thereof wasabout 220.

EXAMPLE 4 Emulsifier Production

The procedure of Example 1 was repeated in the same manner except thatthe reaction with allyl glycidyl ether was omitted. Thus was obtained a54% solution of emulsifier E-4 which had no polymerizable unsaturatedgroup. The number-average molecular weight of said emulsifier E-4 was1,200 and the acid value thereof was about 640.

EXAMPLE 5 Emulsifier Production

The same flask as used in Example 1 was charged with 180 parts ofisopropyl alcohol, which was then heated to 80° C. under nitrogen.Thereto was added dropwise over 2 hours a polymerizable monomer mixturecomposed of 144 parts of acrylic acid, 119 parts of Blemmer PE-200 (amethacrylate having the structure ##STR4## product of Nippon Oil andFats Co., Ltd), 36 parts of n-dodecylmercaptan and 0.3 part of AIBN.After completion of the dropping, the mixture was matured under refluxfor 3 hours for driving the polymerization to completion to give a 62%solution of emulsifier E-5. The number average molecular weight of saidemulsifier E-5 was 1,700 and the acid value thereof was about 370.

COMPARATIVE EXAMPLE 1

The procedure of Example 4 was repeated in the same manner except thatthe polymerizable monomer mixture used was composed of 86 parts ofacrylic acid, 139 parts of 2-hydroxyethyl acrylate, 14 parts ofthioglycol and 0.3 part of AIBN. Thus was obtained emulsifier e-1 forcomparison. Said emulsifier e-1 for comparison had an acid value of 280and a number average molecular weight of 1,400. It had no terminallong-chain alkyl group, hence was outside of the scope of the presentinvention.

COMPARATIVE EXAMPLE 2

The procedure of Example 4 was repeated in the same manner except thatthe polymerizable monomer mixture used was composed of 25 parts ofacrylic acid, 106 parts of 2-hydroxyethyl acrylate, 46 parts of methylmethacrylate, 23 parts of dedecylmercaptan and 0.3 part of AIBN. Thuswas obtained emulsifier e-2 for comparison. Said emulsifier e-2 forcomparison had an acid value of 96, hence was outside the scope of thepresent invention.

EXAMPLE 6 Production of Aqueous Crosslinkable Resin Dispersion

A flask equipped with a dropping funnel, stirrer, nitrogen inlet tube,thermometer and condenser was charged with 146 parts of deionized water,4 parts of the solution of emulsifier E-4 as obtained in Example 4 and1.6 parts of 28% aqueous ammonia, and the resultant mixture was heatedat 65° C. in a gentle nitrogen gas stream. Thereinto was poured 4 partsof a 5% aqueous solution of 2,2'-azobis(2-amidinopropane)dihydrochloride. Then, a monomer composition prepared in advance andcomposed of 47 parts of methyl methacrylate, 50 parts of ethyl acrylateand 3 parts of glycidyl methacrylate was added dropwise from thedropping funnel over 2 hours. After completion of the dropping, stirringwas continued for 1 hour while the temperature was maintained at 65° C.The reaction mixture was then cooled to give a crosslinkableresin-containing aqueous dispersion R-1 with a nonvolatile mattercontent of 39.8%.

EXAMPLES 7-24 AND COMPARATIVE EXAMPLES 3-17 Production of AqueousCrosslinkable Resin Dispersions

Aqueous crosslinkable resin dispersions R-2 to R-19 and aqueous resindispersions r-1 to r-13 for comparison were obtained by repeating theprocedure of Example 6 in the same manner except that the kind andamount of emulsifier and the monomer components were changed as shown inTables 1--1 to 1-3.

In Comparative Examples 16 and 17, in which emulsifiers e-1 and e-2 forcomparison were respectively used as the emulsifier, aggregates formedin large amounts in the course of emulsion polymerization and thereforethe polymerization could not be continued any longer.

                                      TABLE 1-1                                   __________________________________________________________________________    Aqueous                                                                       crosslinkable                                                                 resin                         Emulsifier Nonvolatile                          No.   dispersion                                                                           Monomer components (parts)                                                                     No.                                                                              Amount (parts)                                                                        matter (%)                           __________________________________________________________________________    Example 6                                                                           R-1    Methyl methacrylate                                                                          47                                                                              E-4                                                                              4       39.8                                              Ethyl acrylate 50                                                             Glycidyl methacrylate                                                                        3                                                 Example 7                                                                           R-2    Styrene        68                                                                              E-1                                                                              6       40.1                                              Butyl acrylate 28                                                             2-Isopropenyl-2-oxazoline                                                                    4                                                 Example 8                                                                           R-3    Methyl methacrylate                                                                          60                                                                              E-2                                                                              10      40.6                                              2-Ethylhexyl acrylate                                                                        34                                                             2-Aziridinylethyl methacrylate                                                               1                                                              Vinyltriethoxysilane                                                                         5                                                 Example 9                                                                           R-4    Methyl methacrylate                                                                          66                                                                              E-3                                                                              5       40.2                                              Butyl acrylate 26                                                             Glycidyl methacrylate                                                                        5                                                              Vinyltrimethoxysilane                                                                        3                                                 Example 10                                                                          R-5    Methyl methacrylate                                                                          42                                                                              E-4                                                                              8       40.0                                              Ethyl acrylate 56                                                             2-Aziridinylethyl methacrylate                                                               2                                                 Example 11                                                                          R-6    Methyl methacrylate                                                                          35                                                                              E-3                                                                              4       39.9                                              Styrene        30                                                             Butyl acrylate 32                                                             Glycidyl methacrylate                                                                        3                                                 Example 12                                                                          R-7    Methyl methacrylate                                                                          60                                                                              E-2                                                                              6       40.2                                              Butyl acrylate 36                                                             Glycidyl methacrylate                                                                        2                                                              Vinyltrimethoxysilane                                                                        2                                                 Example 13                                                                          R-8    Ethyl acrylate 98                                                                              E-5                                                                              10      40.6                                              Glycidyl methacrylate                                                                        2                                                 Example 14                                                                          R-9    Vinyl acetate  15                                                                              E-1                                                                              6       40.2                                              Styrene        15                                                             Butyl acrylate 66                                                             2-Vinyl-2-oxazoline                                                                          4                                                 Example 15                                                                          R-10   Methyl methacrylate                                                                          35                                                                              E-2                                                                              5       40.2                                              Butyl acrylate 60                                                             2-Aziridinylethyl methacrylate                                                               2                                                              Vinyltriethoxysilane                                                                         3                                                 Example 16                                                                          R-11   Butyl acrylate 99                                                                              E-1                                                                              9       40.3                                              Glycidyl methacrylate                                                                        1                                                 __________________________________________________________________________

                                      TABLE 1-2                                   __________________________________________________________________________            Aqueous                                                                       crosslinkable                                                                 resin                           Emulsifier      Nonvolatile           No.     dispersion                                                                            Monomer components (parts)                                                                            No.    Amount (parts)                                                                         matter                __________________________________________________________________________                                                            (%)                   Example 17                                                                            R-12    Vinyl acetate       5   E-4    12       41.0                                  Butyl acrylate      93.5                                                      2-isopropenyl-2-oxazoline                                                                         1.5                                       Example 18                                                                            R-13    Vinyl acetate       5   E-3    14       40.0                                  2-Ethylhexyl acrylate                                                                             94.3                                                      2-Aziridinylethyl methacrylate                                                                    0.3                                                       Vinyltrimethoxysilane                                                                             0.4                                       Example 19                                                                            R-14    Methyl methacrylate 38  E-4    7        40.4                                  Ethyl acrylate      50                                                        Glycidyl methacrylate                                                                             12                                        Example 20                                                                            R-15    Styrene             50  E-1    12       40.3                                  Butyl acrylate      40                                                        2-Isopropenyl-2-oxazoline                                                                         8                                                         γ-Methacryloyloxypropyltrimethoxysilane                                                     2                                         Example 21                                                                            R-16    Acrylonitirile      10  E-2    6        40.7                                  Methyl methacrylate 53                                                        Butyl acrylate      31                                                        Ethylene glycol dimethacrylate                                                                    2                                                         2-Aziridinylethyl methacrylate                                                                    3                                                         Vinyltrimethoxysilane                                                                             1                                         Example 22                                                                            R-17    Styrene             15  E-4    18       40.7                                  Methyl acrylate     83                                                        2-Isopropenyl-2-oxazoline                                                                         2                                         Example 23                                                                            R-18    Methyl methacyrlate 27  E-3    5        40.1                                  Ethyl acrylate      66                                                        Glycidyl methacrylate                                                                             2                                                         γ-Methacryloyloxypropyltrimethoxysilane                                                     5                                         Example 24                                                                            R-19    Methyl methacrylate 39  E-5    9        40.6                                  Buthyl acrylate     49                                                        Glycidyl methacrylate                                                                             2                                                         Vinyltrimethoxyethoxysilane                                                                       10                                        Comparative                                                                           r-1 for Methyl methacrylate 47  Sodium dode-                                                                         3        40.5                  Example 3                                                                             comparison                                                                            Ethyl acrylate      50  cylbenzene-                                           Glycidyl methacrylate                                                                             3   sulfonate                             Comparative                                                                           r-2 for Methyl methacrylate 35  Sodium 2        40.3                  Example comparison                                                                            Styrene             30  dodecyl                                               Butyl acrylate      32  sulfate                               __________________________________________________________________________

                                      TABLE 1-3                                   __________________________________________________________________________            Aqueous                                                                       crosslinkable                                                                 resin                          Emulsifier       Nonvolatile           No.     dispersion                                                                            Monomer components (parts)                                                                           No.     Amount (parts)                                                                         matter                __________________________________________________________________________                                                            (%)                   Comparative                                                                           r-3 for Vinyl acetate       15 Nonipol 8        41.3                  Example 5                                                                             comparison                                                                            Styrene             15 400                                                    Butyl acrylate      66 (Note 1)                                               2-Vinyl-2-oxazoline 4                                         Comparative                                                                           r-4 for Butyl acrylate      99 Sodium dode-                                                                          2        40.3                  Example 6                                                                             comparison                                                                            Glycidyl methacrylate                                                                             1  cylbenzene-                                                                   sulfate                                Comparative                                                                           r-5 for Methyl methacrylate 38 Sodium  2        40.2                  Example 7                                                                             comparison                                                                            Ethyl acrylate      50 dodecyl                                                Glycidyl methacrylate                                                                             12 sulfate                                Comparative                                                                           r-6 for Methyl methacrylate 27 Sodium  2        40.2                  Example 8                                                                             comparison                                                                            Ethyl acrylate      66 dodecyl                                                Glycidyl methacrylate                                                                             2  sulfate                                                γ-Methacryloyloxypropyltrimethoxysilane                                                     5                                         Comparative                                                                           r-7 for Methyl methacrylate 50 E-4     4        40.0                  Example 9                                                                             comparison                                                                            Ethyl acrylate      50                                        Comparative                                                                           r-8 for Methyl methacrylate 35 E-3     4        40.0                  Example 10                                                                            comparison                                                                            Styrene             30                                                        Butyl acrylate      35                                        Comparative                                                                           r-9 for Vinyl acetate       15 E-1     6        40.1                  Example 11                                                                            comparison                                                                            Styrene             15                                                        Butyl acrylate      70                                        Comparative                                                                           r-10 for                                                                              Butyl acrylate      100                                                                              E-1     9        40.3                  Example 12                                                                            comparison                                                            Comparative                                                                           r-11 for                                                                              Methyl methacrylate 45 E-4     7        40.1                  Example 13                                                                            comparison                                                                            Ethyl acrylate      55                                        Comparative                                                                           r-12 for                                                                              Methyl methacrylate 30 E-3     5        40.2                  Example 14                                                                            comparison                                                                            Ethyl acrylate      70                                        Comparative                                                                           r-13 for                                                                              Methyl methacrylate 30 E-4     10       40.2                  Example 15                                                                            comparison                                                                            Butyl acrylate      20                                                        Glycidyl methacrylate                                                                             50                                        Comparative                                                                           --      Methyl methacrylate 50 e-1 for 10       --                    Example 16                                                                            (No resin                                                                             Butyl acrylate      47 com-                                           dispersion                                                                            Glycidyl methacrylate                                                                             3  parison                                        obtained)                                                             Comparative                                                                           --      Methyl methacrylate 50 e-2 for 10       --                    Example 17                                                                            (No resin                                                                             Butyl acrylate      47 com-                                           dispersion                                                                            Glycidyl methacrylate                                                                             3  parison                                        obtained)                                                             __________________________________________________________________________     (Note 1)                                                                      Nonipol 400: Ethylene oxide adduct of nonylphenol, product of Sanyo           Chemical Industries, Ltd.                                                

EXAMPLE 25 Production of Aqueous Crosslinkable Resin Dispersion

The same flask as used in Example 6 was charged with 146 parts ofdeionized water, 4 parts of the solution of emulsifier E-4 and 1.6 partsof 28% aqueous ammonia, and the temperature was raised to 70° C. in agentle nitrogen gas stream. Thereinto was poured 6 parts of a 5% aqueoussolution of 4,4'-azobis(4-cyanopentanoic acid) and, then, a firstmonomer composition prepared in advance and composed of 23 parts ofmethyl methacrylate, 25 parts of ethyl acrylate and 2 parts of glycidylmethacrylate was added dropwise over 1 hour. After 30 minutes ofstirring, a second polymerizable monomer mixture composed of 23 parts ofmethyl methacrylate, 25 parts of ethyl acrylate, and 2 parts ofvinyltrimethoxysilane was added dropwise over 1 hour. After a furtherhour of stirring, the reaction mixture was cooled to give an aqueouscrosslinkable resin dispersion, R-20, with a nonvolatile matter contentof 39.8%.

EXAMPLES 26 AND 27

Aqueous crosslinkable resin dispersions R-21 and R-22 were obtained byrepeating the procedure of Example 25 in the same manner except that theemulsifier and first and second monomer compositions used wererespectively as shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________         Aqueous                                                                       crosslinkable                                                            Example                                                                            resin                   Emulsifier   Nonvolatile                         No.  dispersion                                                                           Monomer components (parts)                                                                       No.                                                                              Amount (parts)                                                                        matter (%)                          __________________________________________________________________________    25   R-20   First monomer composition                                                                        E-4                                                                              4       39.8                                            Methyl methacrylate                                                                            23                                                           Ethyl acrylate   25                                                           Glycidyl methacrylate                                                                          2                                                            Second monomer composition                                                    Methyl methacrylate                                                                            23                                                           Ethyl acrylate   25                                                           Vinyltrimethoxysilane                                                                          2                                                26   R-21   First monomer composition                                                                        E-1                                                                              9       40.4                                            Methyl methacrylate                                                                            25                                                           Ethyl acrylate   7                                                            Glycidyl methacrylate                                                                          1                                                            Second monomer composition                                                    Methyl methacrylate                                                                            22                                                           Ethyl acrylate   42                                                           γ-Methacryloyloxypropyltri-                                                              3                                                            methoxysilane                                                     27   R-22   First monomer composition                                                                        E-1                                                                              10      40.5                                            Methyl methacrylate                                                                            28                                                           Ethyl acrylate   37                                                           Trimethylolpropane trimethacrylate                                                             1                                                            Glycidyl methacrylate                                                                          1                                                            Second monomer composition                                                    Acrylonitrile    7                                                            Methyl methacrylate                                                                            14                                                           Butyl acrylate   11                                                           Vinlytrimethoxysilane                                                                          1                                                __________________________________________________________________________

EXAMPLES 28-34 Production of Aqueous Compositions

Aqueous compositions L-1 to L-7 were obtained by uniformly blending withstirring the corresponding aqueous crosslinkable resin dispersions andfine particle materials shown in Table 3 in a flask equipped with astirrer at room temperature.

                  TABLE 3                                                         ______________________________________                                                                                Non-                                                 Aqueous                  vola-                                       Aqueous  crosslinkable                                                                             Fine particle                                                                              tile                                  Ex-   compo-   resin dispersion                                                                          material     mat-                                  ample sition          Amount Species Amount ter                               No.   No.      No.    (parts)                                                                              (Note 1)                                                                              (parts)                                                                              (%)                               ______________________________________                                        28    L-1      R-1    250    Snowtex C                                                                              25    38.0                              29    L-2      R-3    250    Snowtex C                                                                              50    37.5                              30    L-3      R-7    250    Snowtex C                                                                             100    34.5                              31    L-4      R-21   250    Titania sol                                                                           600    15.3                              32    L-5      R-16   250    Snowtex C                                                                             250    30.1                              33    L-6      R-22   250    Snowtex C                                                                             350    28.5                              34    L-7      R-18   250    Snowtex C                                                                              50    36.7                              ______________________________________                                    

(Note 1) Species of fine particle material

Snowtex C: A 20% aqueous dispersion of silica particles 10-20 nm indiameter; product of Nissan Chemical Industries.

Titania sol: A hydrosol containing 5% of titania particles 2-3 nm indiameter.

EXAMPLE 35 Production of Aqueous Composition

The same flask as used in Example 6 was charged with 146 parts ofdeionized water, 5 parts of the solution of emulsifier E-3 as obtainedin Example 3, 25 parts of Snowtex C and 1.6 parts of 28% aqueousammonia, and the contents were heated to 65° C. in a gentle nitrogen gasstream. Thereinto was poured 4 parts of a 5% aqueous solution of2,2'-azobis(2-amidinopropane) dihydrochloride and then, a monomercomposition prepared in advance and composed of 61 parts of methylmethacrylate, 26 parts of butyl acrylate, 51 parts of glycidylmethacrylate and 3 parts of vinyltrimethoxysilane was added dropwisefrom the dropping funnel over 2 hours. After completion of the dropping,stirring was continued for 1 hour while the temperature was maintainedat 65° C. Then, the mixture was cooled to give an aqueous composition,L-8, with a nonvolatile matter content of 38.2%.

EXAMPLE 36 Production of Aqueous Composition

The procedure of Example 35 was repeated in the same manner except thatSnowtex was used in an amount of 100 parts and that the monomercomposition used in this example was composed of 60 parts of methylmethacrylate, 33 parts of butyl acrylate, 2 parts of glycidylmethacrylate and 5 parts of vinyltriethoxysilane. Thus was obtained anaqueous composition, L-9, with a nonvolatile matter content of 34.3%.

EXAMPLE 37 Production of Aqueous Composition

The same flask as used in Example 6 was charged with 146 parts ofdeionized water, 12 parts of the solution of emulsifier E-4 as obtainedin Example 1 and 1.6 parts of 28% aqueous ammonia, and the contents wereheated to 65° C. in a gentle nitrogen gas stream. Thereinto was poured 4parts of a 5% aqueous solution of 2,2'-azobis(2-amidinopropane)dihydrochloride. Then, a monomer composition prepared in advance andcomposed of 20 parts of styrene, 30 parts of metyl methacrylate, 40parts of butyl acrylate, 8 parts of 2-isopropenyl-2-oxazoline and 2parts of γ-methacryloyloxypropyltrimethoxysilane was added dropwise fromthe dropping funnel over 2 hours. Thereafter, 250 parts of Snowtex C wasadded, stirring was continued for 2 hours at 65° C., and the mixture wascooled to give an aqueous composition, L-10, with a nonvolatile mattercontent of 30.0%.

EXAMPLE 38 Production of Aqueous Composition

An aqueous composition, L-11, having a nonvolatiIe matter content of35.4% was obtained by repeating the procedure of Example 37 in the samemanner except that Snowtex C was used in an amount of 75 parts and thatthe monomer composition used was composed of 39 parts of methylmethacrylate, 44 parts of butyl acrylate, 5 parts of 2-hydroxyethylacrylate, 2 parts of glycidyl methacrylate and 10 parts ofvinyltrimethoxysilane.

EXAMPLES 39-44 Production of Aqueous Resin Compositions

The aqueous crosslinkable resin dispersion and polyvinyl alcohol species(10% aqueous solution) each specified in Table 4 were uniformly mixedtogether at room temperature by sufficient stirring. Thus were obtainedaqueous resin compositions M-1 to M-6.

                  TABLE 4                                                         ______________________________________                                                                                Non-                                                 Aqueous                  vola-                                       Aqueous  crosslinkable                                                                             10% Polyvinyl                                                                              tile                                  Ex-   compo-   resin dispersion                                                                          alcohol      mat-                                  ample sition          Amount         Amount ter                               No.   No.      No.    (parts)                                                                              Species*                                                                              (parts)                                                                              (%)                               ______________________________________                                        39    M-1      R-1    250    Kuraray 20     37.5                                                           Poval 117                                        40    M-2      R-5    250    Kuraray  5     39.3                                                           Poval 117                                        41    M-3      R-7    250    Kuraray 10     38.8                                                           Poval 217                                        42    M-4      R-14   250    Kuraray 200    26.4                                                           Poval 217                                        43    M-5      R-16   250    Kuraray 400    21.5                                                           Poval 205                                        44    M-6      R-20   250    Kuraray 10     38.7                                                           Poval 117                                        ______________________________________                                         *Species of polyvinyl alcohol                                            

Kuraray Poval 117: Completely saponified product, degree ofpolymerization 1,700

Kuraray Poval 217: Partially saponified product, degree ofpolymerization 1,700

Kuraray Poval 205: Partially saponified product, degree ofpolymerization 500

(Each is a product of Kuraray Co., Ltd.)

EXAMPLES 45-47 Production of Aqueous Resin Composition

The same flask as used in Example 6 was charged with the aqueouscrosslinkable resin dispersion and 10% aqueous polyvinyl alcoholsolution each specified in Table 5, and the temperature was raised to70° C. with stirring in a gentle nitrogen gas stream. Thereto was added2 parts of a 5% aqueous solution of ammonium persulfate, stirring wasthen continued at 65° C. for 2 hours, and the mixture was cooled. Thuswere obtained aqueous resin compositions M-7 to M-9.

                  TABLE 5                                                         ______________________________________                                                                                Non-                                                 Aqueous                  vola-                                       Aqueous  crosslinkable                                                                             10% Polyvinyl                                                                              tile                                  Ex-   compo-   resin dispersion                                                                          alcohol      mat-                                  ample sition          Amount         Amount ter                               No.   No.      No.    (parts)                                                                              Species (parts)                                                                              (%)                               ______________________________________                                        45    M-7      R-2    250    Kuraray  20    37.6                                                           Poval 117                                        46    M-8      R 250  Kuraray                                                                                5     39.4                                                                  Poval 217                                        47    M-9      R-22   250    Kuraray 1000   26.5                                                           Poval 217                                        ______________________________________                                    

EXAMPLE 48 Production of Aqueous Resin Composition

The same flask as used in Example 6 was charged with 146 parts ofdeionized water, 10 parts of the solution of emulsifier E-5 as obtainedin Example 5 and 1.6 parts of 28% aqueous ammonia, and the contents wereheated to 65° C. in a gentle nitrogen gas stream. Thereinto was poured 4parts of a 5% aqueous solution of 2,2'-azobis(2-amidinopropane)dihydrochloride. Then, a monomer composition prepared in advance andcomposed of 39 parts of methyl methacrylate, 49 parts of butyl acrylate,2 parts of 2-aziridinylethyl methacrylate and 10 parts ofvinyltriethoxysilane was added dropwise from the dropping funnel over 2hours. Thereto was then added 10 parts of a 10% aqueous solution ofKuraray Poval 117, and the resultant mixture was stirred at 65° C. for 2hours. The subsequent cooling gave an aqueous resin composition, M-10,with a nonvolatile matter content of 38.8%.

EXAMPLES 49-54 Production of Water-Dispersible Compositions

A flask equipped with a stirrer was charged with the aqueouscrosslinkable resin disperison or aqueous composition or aqueous resincomposition, polyvinyl alcohol and fine-particle material each specifiedin Table 6, and the contents were stirred at room temperaturesufficiently to give a uniform mixture. Thus were obtainedwater-dispersible compositions N-1 to N-6.

                                      TABLE 6                                     __________________________________________________________________________         Water-                                    Non-                                dispesible                       Amount of fine-                                                                        volatile                       Example                                                                            composi-                                                                           Amount of aqueous crosslinkable                                                               Amount of 10% poly-                                                                       particle material                                                                      matter                         No.  tion No.                                                                           resin dispersion, etc. (parts)                                                                vinyl alcohol (parts)                                                                     (parts)  (%)                            __________________________________________________________________________    49   N-1  Aqueous crosslinkable resin                                                                   Kuraray Poval 117:20                                                                      Snowtex C:25                                                                           36.2                                     dispersion R-1:250                                                  50   N-2  Aqueous composition L-9:350                                                                   Kuraray Poval 117:5                                                                       --       33.9                           51   N-3  Aqueous resin composition                                                                     --          Titania sol:400                                                                        18.4                                     M-8:255                                                             52   N-4  Aqueous crosslinkable resin                                                                   Kuraray Poval 217:200                                                                     Snowtex C:150                                                                          25.0                                     dispersion R-22:250                                                 53   N-5  Aqueous resin composition                                                                     --          Snowtex C:100                                                                          25.2                                     M-9:450                                                             54   N-6  Aqueous crosslinkable resin                                                                   Kuraray Poval 205:30                                                                      Snowtex C:50                                                                           34.2                                     composition M-18:250                                                __________________________________________________________________________

EXAMPLE 55 Testing of Films for Water Resistance

Cast films were prepared from several of the dispersions according tothe present invention as obtained in the foregoing examples and testedfor water resistance. The results obtained are shown in Table 7. Filmpreparation

The dispersion according to the invention was cast onto a teflon plateto a dry thickness of 0.2-0.3 mm and dried at 20° C. for 1 day. The filmthus formed was heated at 130° C. for 3 minutes and used as the testfilm.

Test Method

Water resistance: A square test specimen (about 20 mm×about 20 mm) wascut from the test film and weighed (W₀) It was immersed in deionizedwater for 3 days, then taken up, wiped lightly to remove the moisture onthe surface, and weighed (W₁). It was dried at 100° C. for 1 hour, thenallowed to cool, and weighed (W₂)

The water resistance of the test film was evaluated in terms of thepercent water absorption and percent dissolution calculated as follows:##EQU1##

Film appearance: The film immersed in deionized water for 3 days wasevaluated for transparency. The symbols ◯, Δ and × given in Table 7respectively have the following meanings:

◯..... Tranparent; no change.

Δ..... Semitransparent

×.... Whitening

                  TABLE 7                                                         ______________________________________                                                          Water     Dis-     Film                                     Aqueous dispersion etc.                                                                         absorption                                                                              solution appear-                                  used for film formation                                                                         (%)       (%)      ance                                     ______________________________________                                        Aqueous crosslinkable resin                                                                     10.7      0.2      Δ                                  dispersion R-1                                                                Aqueous crosslinkable resin                                                                     8.0       0.2      ∘-Δ                    dispersion R-3                                                                Aqueous crosslinkable resin                                                                     7.8       0.1      ∘-Δ                    dispersion R-4                                                                Aqueous crosslinkable resin                                                                     10.6      0.1      Δ                                  dispersion R-5                                                                Aqueous crosslinkable resin                                                                     9.5       0.2      ∘-Δ                    dispersion R-15                                                               Aqueous crosslinkable resin                                                                     10.6      0.2      Δ                                  dispersion R-17                                                               Aqueous crosslinkable resin                                                                     6.5       0.1      ∘                            dispersion R-20                                                               Aqueous composition L-1                                                                         7.7       0.1      ∘-Δ                    Aqueous composition L-5                                                                         7.6       0.1      ∘                            Aqueous composition L-9                                                                         5.1       0.1      ∘                            Aqueous resin composition M-3                                                                   8.1       0.2      ∘-Δ                    Aqueous resin composition M-8                                                                   7.5       0.1      ∘                            Water-dispersible composition                                                                   6.3       0.1      ∘                            M-1                                                                           Water-dispersible composition                                                                   5.9       0.1      ∘                            M-2                                                                           Water-dispersible composition                                                                   4.8       0.1      ∘                            M-6                                                                           Aqueous crosslinkable resin                                                                     50.5      0.9      x                                        dispersion (for comparison) r-1                                               Aqueous crosslinkable resin                                                                     68.5      1.2      x                                        dispersion (for comparison) r-3                                               Aqueous crosslinkable resin                                                                     22.3      0.5      x                                        dispersion (for comparison) r-7                                               Aqueous crosslinkable resin                                                                     35.3      0.2      x                                        dispersion (for comparison) r-15                                              ______________________________________                                    

EXAMPLE 56 Coating Compositions to be Applied to Inorganic Substrates

The aqueous dispersions and other compositions according to theinvention were tested for their performance as coating compositions forinorganic substrates.

Water Resistance Testing as Primers for Colored Pavements

The aqueous dispersions and other compositions according to theinvention were each applied uniformly to a 5-mm-thick slate plate in anamount of about 100 g/m² by means of a flat brush. After 2 hours ofdrying at room temperature, a mixed paint obtained by mixing a coloredpaint (Nippoly-Color®R-1; product of Nippon Polyester) with No. 7 silicasand in a weight ratio of 1:1 was applied to the plate in an amount ofabout 1,000 g/m² by means of a trowel. The coated slate plate was driedfor 7 days under conditions of 20° C. and 65% RH (relative humidity) togive a test specimen.

The thus-obtained test specimens, in the original state and afterimmersion in water, were measured for bond strength according to JIS A6910. The bond strength after immersion in water was measured afterimmersion of the test specimen in water at room temperature for 24 hoursand the subsequent air drying for 2 hours.

The test results are shown in Table 8. In the operation of coating theslate plates with the dispersion or the like by means of the brush,foaming was slight and the operation was easy with any of the aqueousdispersions and other compositions according to the invention andfoam-free paint surfaces were obtained. On the contrary, the aqueousresin dispersion r-1 for comparison often foamed readily, was difficultto handle, and tended to allow foams to remain on the painted surface.

                  TABLE 8                                                         ______________________________________                                                       Bond Strength (kg/cm.sup.2)                                                                   After                                                                         immersion                                      Aqueous dispersion etc.                                                                        Original state                                                                              in water                                       ______________________________________                                        Aqueous crosslinkable resin                                                                    10.8 (Slate broken)                                                                         7.1                                            dispersion R-1                                                                Aqueous crosslinkable resin                                                                    10.9 (Slate broken)                                                                         7.7                                            dispersion R-2                                                                Aqueous crosslinkable resin                                                                    11.0 (Slate broken)                                                                         8.2                                            dispersion R-3                                                                Aqueous crosslinkable resin                                                                    10.9 (Slate broken)                                                                         8.4                                            dispersion R-4                                                                Aqueous crosslinkable resin                                                                    11.2 (Slate broken)                                                                         9.1                                            dispersion R-20                                                               Aqueous composition L-1                                                                        10.6 (Slate broken)                                                                         8.4                                            Aqueous composition L-2                                                                        10.8 (Slate broken)                                                                         8.9                                            Aqueous composition L-8                                                                        10.8 (Slate broken)                                                                         9.0                                            Aqueous resin composition M-1                                                                  10.7 (Slate broken)                                                                         8.2                                            Aqueous resin composition M-7                                                                  10.5 (Slate broken)                                                                         8.5                                            Water-dispersible composi-                                                                     10.9 (Slate broken)                                                                         9.0                                            tion N-1                                                                      Aqueous resin composition                                                                      10.0 (Slate broken)                                                                         1.2                                            (for comparison) r-1                                                          Aqueous resin composition                                                                      10.1 (Slate broken)                                                                         3.5                                            (for comparison) r-7                                                          ______________________________________                                    

EXAMPLE 57 Overcoating Compositions for Heat-Sensitive Recording PaperSheets

The coating compositions shown in Table 9 were prepared by using theaqueous dispersions and other compositions according to the inventionand adding thereto a filler (in each case, kaolinite clay) and acrosslinking agent. The aqueous dispersions and other compositionsaccording to the invention were used each in an amount of 100 parts asthe nonvolatile matter.

                                      TABLE 9                                     __________________________________________________________________________    Coating            Filler                                                                            Crosslinking agent                                     composition        amount          Amount                                     No.   Aqueous dispersion etc.                                                                    (parts)                                                                           Kind        (parts)                                    __________________________________________________________________________    I     Aqueous crosslinkable                                                                      50  Water-soluble methylol                                                                    10                                               resin dispersion R-14                                                                          melamine                                               II    Aqueous crosslinkable                                                                      50  Water-soluble methylol                                                                    10                                               resin dispersion R-15                                                                          melamine                                               III   Aqueous crosslinkable                                                                      50  Water-soluble methylol                                                                    10                                               resin dispersion R-16                                                                          melamine                                               IV    Aqueous crosslinkable                                                                      50  Water-soluble methylol                                                                    10                                               resin dispersion R-22                                                                          melamine                                               V     Aqueous composition L-5                                                                    40  Water-soluble methylol                                                                    10                                                                melamine                                               VI    Aqueous composition L-6                                                                    40  Water-soluble methylol                                                                    10                                                                melamine                                               VII   Aqueous composition L-10                                                                   45  Water-soluble methylol                                                                    10                                                                melamine                                               VIII  Aqueous resin composition                                                                  50  Glyoxal     10                                               M-1                                                                     IX    Aqueous resin composition                                                                  50  Glyoxal     10                                               M-5                                                                     X     Aqueous resin composition                                                                  50  Boric acid  0.5                                              M-9                                                                     XI    Water-dispersible                                                                          45  Boric acid  0.5                                              composition N-4                                                         XII   Water-dispersible                                                                          45  Boric acid  0.5                                              composition N-5                                                         I for Aqueous resin dispersion                                                                   50  Water-soluble methylol                                                                    10                                         comparison                                                                          (for comparison) r-5                                                                           melamine                                               II for                                                                              Aqueous resin dispersion                                                                   50  Water-soluble methylol                                                                    10                                         comparison                                                                          (for comparison) r-11                                                                          melamine                                               __________________________________________________________________________

Heat-sensitive recording paper sheets were then prepared in thefollowing manner, with synthetic paper sheets as the supporing members:

    ______________________________________                                        ]Liquid composition A]                                                        3-N-Methyl-N-cyclohexylamino-                                                                          300 parts                                            6-methyl-7-anilinofluoran                                                     10% Aqueous solution of  300 parts                                            polyvinyl alcohol                                                             Water                    400 parts                                            [Liquid composition B]                                                        4,4'-Isopropylidenebis(2,6-                                                                            300 parts                                            dibromophenol)                                                                10% Aqueous solution of  200 parts                                            polyvinyl alcohol                                                             Water                    400 parts                                            [Liquid composition C]                                                        di-o-chlorophenyl adipate                                                                              100 parts                                            Calcium carbonate        300 parts                                            10% Aqueous solution of  200 parts                                            polyvinyl alcohol                                                             Water                    300 parts                                            ______________________________________                                    

The above compositions were each treated in a sand mill for obtaining adispersion of a particle size of 0.8±0.1 μm. A coating composition forheat-sensitive color-developing layer formation was prepared from thethus-obtained liquid compositions or dispersions A, B and C by mixing 20parts of liquid composition A, 70 parts of liquid composition B and 10parts of liquid composition C together. The coating composition was thenapplied to a synthetic paper sheet (Yupo FPG 80; product of Oji-YukaSynthetic Paper) made by the film method from a polyolefin-based resinin a coating amount (after drying) of 5 g/m2 by means of a wire barcoater, and dried to give a heat-sensitive color-developing layer.

The coating compositions I to XII and the coating compositions forcomparison I and II were each applied to the surface of theheat-sensitive color-developing layer in an amount (after drying) of 3g/m² by means of a wire bar coater and then dried to give an overcoatlayer.

The overcoat layers thus obtained were treated on a super-calender to asmoothness of 4,000 seconds to give the respective synthetic paper-basedheat-sensitive recording paper sheets. The heat-sensitive recordingpaper sheets thus obtained were measured for sticking resistance,glossiness after allover black color development (incidence angle: 75°),and water resistance.

The results obtained are shown in Table 10. The sticking resistance wasevaluated using a Toshiba Medical model TP8300 printer forultrasonography according to the following criteria:

5: No sticking sound.

4: Almost no sticking sound.

3: Soft sticking sound.

2: Big sticking sound; the coat film is not taken up by the head.

1: Big sticking sound; the coat film is taken up by the head.

For water resistance evaluation, water was dropped on the boundarybetween the color-developed portion (black) and undeveloped portion, theboundary portion was rubbed with a finger, and the extent of migrationof the dye from the color-developed portion was investigated. Thesymbols ◯, Δ and × used in the table respectively have the followingmeanings:

◯: No dissolution from the color-developed portion.

Δ: Slight dissolution from the color-developed portion.

×: Much dissolution from the color-developed portion.

                  TABLE 10                                                        ______________________________________                                        Overcoat                                                                      layer                                                                         coating                        Recording                                                                             Water                                  composi-                                                                             Aqueous dispersion                                                                           Sticking side    resist-                                tion No.                                                                             etc. No.       resistance                                                                             glossiness                                                                            ance                                   ______________________________________                                        I      Aqueous crosslinkable                                                                        3        53      Δ                                       resin dispersion R-14                                                  II     Aqueous crosslinkable                                                                        4        49      ∘-Δ                         resin dispersion R-15                                                  III    Aqueous crosslinkable                                                                        4        52      ∘                                 resin dispersion R-16                                                  IV     Aqueous crosslinkable                                                                        5        50      ∘                                 resin dispersion R-22                                                  V      Aqueous composition                                                                          4        45      ∘                                 L-5                                                                    VI     Aqueous composition                                                                          5        43      ∘                                 L-6                                                                    VII    Aqueous composition                                                                          5        48      ∘                                 L-10                                                                   VIII   Aqueous resin  4        61      ∘-Δ                         composition M-4                                                        IX     Aqueous resin  4        58      ∘                                 composition M-5                                                        X      Aqueous resin  5        60      ∘                                 composition M-9                                                        XI     Water-dispersible                                                                            5        58      ∘                                 composition N-4                                                        XII    Water-dispersible                                                                            5        62      ∘                                 composition N-5                                                        I for  Aqueous resin  1        30      x                                      compari-                                                                             composition                                                            son    (for comparison) r-5                                                   II for Aqueous resin  1        36      Δ-x                              compari-                                                                             composition                                                            son    (for comparison) r-11                                                  ______________________________________                                    

EXAMPLE 58 Coating Compositions to be Applied to Polyester Films

The aqueous dispersions and other compositions were each applied to apolyester film by the in-line coating method to be mentioned below, andthe coat film condition, adhesion and water resistance were evaluated.The results obtained are shown in Table 11.

In-line coating method: Polyethylene terephthalate was melt-extruded andcast onto a cooled rotating drum surface. The cast film was thenstretched 3.5 times in the direction of extrusion (longitudinaldirection), coated with the aqueous dispersion or the like (diluted withwater to a concentration of 3%) by means of a roll coater, stretched 3.5times laterally, namely in the transverse direction, at 105° C., andthermally fixed at 200° C. to give a coated PET film, which had a filmthickness of about 12 μm and a coating layer thickness of about 0.05 μm.

The coated PET films thus obtained were observed for coat filmcondition. Furthermore, test specimens (15×20 cm) were excised fromthem, coated with a polyurethane resin to a thickness (after drying) ofabout 5 μm by means of a bar coater, and dried at 110° C. for 1 minute.The thus-prepared films for testing were tested for adhesion and hotwater resistance.

Coat film appearance: The extent of cissing or crawling was evaluated.The symbols ◯, Δ and × used in the table mean the following:

◯: No cissing or crawling.

Δ: Slight cissing or crawling.

×: Marked cissing or crawling.

Adhesion: A cellophane tape was applied closely to the coated surfaceand then peeled off at a stroke in the direction of 90°, and theadhesion was evaluated in terms of the extent of peeling off of thecoating layer according to the following scoring criteria: 10 points (nopeeling) to 1 point (allover peeling).

Hot water resistance: The coated PET films were immersed in hot water at90-95° C. for 30 minutes, then wiped for removing the surface moisture,and tested for adhesion in the same manner as mentioned above.

                  TABLE 11                                                        ______________________________________                                        Aqueous dispersion etc.                                                                       Film               Hot water                                  No.             appearance                                                                              Adhesion resistance                                 ______________________________________                                        Aqueous crosslinkable resin                                                                   Δ    9       7                                          dispersion R-5                                                                Aqueous crosslinkable resin                                                                   Δ   10       8                                          dispersion R-6                                                                Aqueous crosslinkable resin                                                                   Δ   10       9                                          dispersion R-7                                                                Aqueous crosslinkable resin                                                                   Δ   10       10                                         dispersion R-21                                                               Aqueous composition L-3                                                                       Δ   10       10                                         Aqueous composition L-4                                                                       Δ   10       10                                         Aqueous composition L-9                                                                       Δ   10       10                                         Aqueous resin composi-                                                                        ∘                                                                           10       9                                          tion M-2                                                                      Aqueous resin composi-                                                                        ∘                                                                           10       9                                          tion M-3                                                                      Aqueous resin composi-                                                                        ∘                                                                           10       9                                          tion M-8                                                                      Water-dispersible composi-                                                                    ∘                                                                           10       10                                         tion N-2                                                                      Water-dispersible composi-                                                                    ∘                                                                           10       10                                         tion N-3                                                                      Aqueous resin dispersion                                                                      Δ-x  3       1                                          (for comparison) r-2                                                          Aqueous resin dispersion                                                                      Δ    4       1                                          (for comparison) r-8                                                          Film having no coating layer                                                                  --         1       1                                          ______________________________________                                    

EXAMPLE 59 Coating Compositions to be Applied to Plastics

The aqueous dispersions and other compositions were each applied tovarious plastic plates (2 mm thick; no surface treatment) to a thickness(after drying) of about 10 μm, dried at 80° C. for 10 minutes and testedfor adhesion. The results obtained are shown in Table 12. In the table,the upper row data for each dispersion or composition are adhesion dataobtained in the original state, while the lower row data are adhesiondata obtained after immersion in tap water at room temperature for 24hours.

                  TABLE 12                                                        ______________________________________                                        Aqueous dispersion etc.                                                                             PMMA     PC     ABS                                     No.                   plate    plate  plate                                   ______________________________________                                        Aqueous crosslinkable resin dispersion                                                              9        9      10                                      R-5                   9        8      9                                       Aqueous crosslinkable resin dispersion                                                              10       10     10                                      R-7                   9        9      10                                      Aqueous crosslinkable resin dispersion                                                              10       10     10                                      R-21                  10       10     9                                       Aqueous composition L-3                                                                             10       10     10                                                            9        10     10                                      Aqueous composition L-9                                                                             10       10     10                                                            10       10     10                                      Aqueous resin composition M-8                                                                       10       10     10                                                            9        10     10                                      Water-dispersible composition N-2                                                                   10       10     10                                                            10       10     10                                      Aqueous resin dispersion                                                                            5        6      6                                       (for comparison) r-2  2        1      2                                       Aqueous resin dispersion                                                                            5        7      6                                       (for comparison) r-10 3        2      3                                       ______________________________________                                         PMMA: polymethyl methacrylate                                                 PC: polycarbonate                                                        

EXAMPLE 60 Binders for Nonwoven Fabrics

The aqueous dispersions and other compositions were tested as bindersfor a nonwoven-fabric interlining cloth in the following manner. Theresults are shown in Table 13.

Performance Testing of Nonwoven-Fabric Interlining Cloth TreatingConditions

The aqueous dispersions and other compositions were each diluted withwater to a nonvolatile matter content of 20%. A polyesternonwoven-fabric interlining cloth (weioghing 160 g/m²) was immersed ineach dilution, then squeezed to 80% squeezing, and dried by heating at100° C. for 5 minutes.

Washing Resistance

The feeling was measured by the 45° cantilever method according to JISL-1085 "Methods of testing nowoven-fabric interlining cloths". Thewashing resistance was evaluated in terms of the percentage of feelingretention after 5 washings as calculated relative to the feeling beforewashing. The washing test, too, was performed according to JIS L-1085.

                  TABLE 13                                                        ______________________________________                                                                 Wash-                                                Aqueous dispersion etc. No.                                                                            ability (%)                                          ______________________________________                                        Aqueous crosslinkable resin dispersion R-3                                                             86                                                   Aqueous crosslinkable resin dispersion R-8                                                             80                                                   Aqueous crosslinkable resin dispersion R-10                                                            88                                                   Aqueous composition L-3  90                                                   Aqueous resin composition M-2                                                                          82                                                   Water-dispersible composition N-1                                                                      84                                                   Aqueous resin dispersion (for comparison) r-3                                                          42                                                   Aqueous resin dispersion (for comparison) r-9                                                          53                                                   ______________________________________                                    

EXAMPLE 61 Binders for Flocking

The aqueous crosslinkable resin dispersions were tested as binders forflocking in the following manner. The test results are shown in Table14. Flocked fabric manufacturing conditions

An alkali thickening type thickner and aqueous ammonia were added toeach of the aqueous dispersions and other compositions to adjust theviscosity to 20,000-25,000 cps. A 9A spun rayon twill fabric wasuniformly coated with each composition in a coating amount of 200 g/m²by means of a doctor knife and immediately flocked with 0.6-mm-long1.5-denier rayon piles using an electrostatic flocking machine at avoltage of 30 kV and a pole-to-pole distance of 10 cm. The flockedfabric was then dried by heating at 90° C. for 10 minutes and, aftercooling, the excess piles were removed.

Abrasion Resistance Testing

The test was performed by the JIS L-1084 45R method using a Gaku-Shin(Japan Society for the Promotion of Science) type color abrasionresistance tester. In testing for the abrasion resistance in the statewet with water and the abrasion resistance in the state wet withperclene, the test specimens were immersed in water or perclene for 15minutes and then tested in the wet state. The abrasion resistance wasevaluated in terms of the number of rubbings as required for the basefabric surface to be exposed as a result of falling of piles.

                  TABLE 14                                                        ______________________________________                                                   Abrasion resistance (rubbings)                                     Aqueous crosslinkable                                                                      Original  When wet  When wet                                     resin dispersion No.                                                                       state     with water                                                                              with perclene                                ______________________________________                                        R-8          >1,000    700       550                                          R-9          >1,000    800       700                                          R-10         >1,000    >1,000    900                                          r-3 (for comparison)                                                                          450    100        50                                          r-9             500    110        45                                          ______________________________________                                    

EXAMPLE 62 Carpet Back Coating Compositions

The aqueous crosslinkable resin dispersions were tested as carpet backcoating compositions in the following manner. The results obtained areshown in Table 15.

Treating Conditions

To 100 parts of each aqueous crosslinkable resin dispersion were added30 parts of heavy calcium carbonate and an appropriate amount each of analkali thickening type thickener and aqueous ammonia to give, afteruniformly mixing, a viscosity of about 30,000 cps. The thus-adjusteddispersion was uniformly applied to the back of a tufted carpet(polypropylene split yarn base cloth with nylon piles) in a coatingamount of 1,000 g/m² and then dried by heating at 100° C. for 20 minutesby means of a hot air drier.

Pile Removing Strength

The pile removing strength of each carpet was measured according to JISL-102 "Methods of testing carpets and the like". The pile removingstrength after weathering was measured after allowing the test specimento stand in a sun-shine type weather meter for 1,000 hours and thenallowing it to stand at ordinary temperature for 24 hours.

                  TABLE 15                                                        ______________________________________                                        Aqueous crosslinkable                                                                        Pile removing strength (kg/pile)                               resin dispersion No.                                                                         Original state                                                                            Weather meter                                      ______________________________________                                        R-8            3.1         3.0                                                R-9            3.9         3.5                                                R-10           4.2         4.9                                                r-3 (for comparison)                                                                         1.5         1.1                                                r-9 (for comparison)                                                                         2.3         1.3                                                ______________________________________                                    

EXAMPLE 63 Adhesives for Synthetic Leather-Like Sheet Materials

The aqueous crosslinkable resin dispersions were tested as adhesives forsynthetic leather-like sheet materials. The results are shown in Table16.

Treating Conditions

A solvent-type polyurethane resin was applied to a release paper to athickness of 20 μm and then dried to give a skin layer. Separately, eachaqueous crosslinkable resin dispersion was adjusted to a viscosity ofabout 20,000 cps by adding an alkali thickening type thickener andaqueous ammonia. The dispersion so adjusted was uniformly applied ontothe above-mentioned skin layer in a coating amount of 150 g/m² by meansof a doctor knife. The thus-coated skin layer was immediately broughtinto close contact with a cotton/polyester woven fabric, and theresulting assembly was dried by heating at 100° C. for 5 minutes. Aftercooling, the release paper was peeled off to give a syntheticleather-like sheet material.

Peeling Strength

The peeling strength was measured under the peeling test conditionsdescribed in JIS K-6772. The peeling strength after jungle test wasmeasured after allowing the test specimen to stand in aconstant-temperature, constant-humidity room maintained at 50° C. and atleast 98% relative humidity for 30 days and then allowing it to stand atroom temperature for 24 hours.

                  TABLE 16                                                        ______________________________________                                                      Peel strength (kg/3 cm)                                         Aqueous crosslinkable      After jungle                                       resin dispersion No.                                                                          Original state                                                                           test                                               ______________________________________                                        R-8             4.6        4.2                                                R-9             5.5        5.0                                                R-10            6.0        5.7                                                r-3 (for comparison)                                                                          1.6        1.2                                                r-9 (for comparison)                                                                          1.8        1.5                                                ______________________________________                                    

EXAMPLE 64 Binders for Glass Fibers

The aqueous dispersions and other compositions were each evaluated fortheir performance as internal binders for glass paper and as binders forbundling glass fiber chopped strands. The test methods used aredescribed below and the results are shown in Table 17.

Test Methods

(1) Binders for glass paper

1) Preparation of glass paper

Glass fibers, 4 μm in fiber diameter, were beated by a conventionalmethod and dispersed in water in a concentration of 1 g/liter. To thedispersion was added with stirring the aqueous dispersion or the like inan amount of 15% (on the nonvolatile matter basis) relative to the glassfiber weight. Then, Accofloc C470 (Mitsui-Cyanamid's macromolecularcationic flocculant) was added to cause flocculation of the system, andthe flocculated mass was subjected to papermaking. The sheet obtainedwas dried at 150° C. for 5 minutes to give a glass paper sheet with abasis weight of about 100 g.

2) Tensile strength of glass paper

The glass paper sheet was cut to 2.5-cm-wide strips and these weretested for tensile strength in the dry state and in the wet state afterimmersion in water at room temperature for 24 hours using an Instronuniversal tester.

(2) Binders for bundling

1) Preparation of chopped strands

The dispersion to be tested was diluted with water to a nonvolatilematter content of 5%. To 100 parts of this diluted dispersion were added1.5 parts of a polyoxyethylenesorbitan fatty acid ester (Kao Chemical'sTween 80) as lubricant and 0.5 part of γ-aminopropyltriethoxysilane ascoupling agent. The thus-obtained binder (bundling liquid) was appliedto melt-spun E glass fibers on a rotating roll, and the binder-coatedglass fibers were bundled together, then cut to a length of about 6 mmand dried to give chopped strands.

2) Collectivity of chopped strands

The chopped strands obtained were evaluated by the eye for the extent ofcracking. The symbols ⊚, ◯, Δ and × used in the table mean that theoccurrence of cracking was respectively as follows:

⊚: No occurrence.

◯: A few cracks.

Δ: A rather large number of cracks.

×: A very large number of cracks.

                  TABLE 17                                                        ______________________________________                                                        Glass fiber paper                                                             tensile strength                                                                          Chopped                                                           (kg/2.5 cm) strand                                            Aqueous dispersion etc.                                                                         Dry      Wet      conver-                                   No.               strength strength gency                                     ______________________________________                                        Aqueous crosslinkable resin                                                                     3.6      2.4      ∘                             dispersion R-17                                                               Aqueous crosslinkable resin                                                                     3.9      2.5      ∘                             dispersion R-18                                                               Aqueous crosslinkable resin                                                                     4.3      2.7      ⊚                          dispersion R-19                                                               Aqueous composition L-7                                                                         4.7      2.8      ⊚                          Aqueous composition L-11                                                                        4.9      3.1      ⊚                          Aqueous resin composition M-6                                                                   5.0      2.7      ⊚-∘            Aqueous resin composition M-10                                                                  5.1      2.5      ⊚                          Water-dispersible 5.0      3.3      ⊚                          composition N-6                                                               Aqueous resin composition                                                                       3.5      0.6      Δ-x                                 (for comparison) r-6                                                          Aqueous resin composition                                                                       3.3      0.1      x                                         (for comparison) r-12                                                         ______________________________________                                    

Note) In the processes of glass paper making and chopped strandproduction, foaming occurred only to a slight extent and handling waseasy with the aqueous dispersions and other compositions according tothe invention, whereas, with the aqueous resin dispersion r-1 forcomparison, foaming was significant and handling was difficult.

EXAMPLE 65 Adhesives for Paper Labels

The aqueous crosslinkable resin dispersions and the aqueous resindispersions for comparison were each applied to a release paper to athickness (after drying) of 15-20 μm. After drying at 100° C. for 2minutes, the adhesive layer was transferred from the release paper to acoat paper sheet by bringing the latter into close contact with therelease paper, whereby a paper label to serve as a test specimen wasprepared. The paper label test specimens obtained in that manner weretested for physical properties by the methods described below. As aresult, it was found that the aqueous crosslinkable resin dispersionsR-11 to R-13 are very excellent in initial physical characteristics,such as ball tack, adhesion and holding power, and that these physicalcharacteristics do not decrease even after storage underhigh-temperature, high-humidity conditions, hence said dispersions givegood moisture resistance. On the contrary, the aqueous resin dispersionsr-4 and r-10 for comparison underwent marked decreases in such physicalproperties as ball tack, adhesion and holding power during storage underhigh-temperature, high-humidity conditions, hence were very poor inmoisture resistance. More detailed results are shown in Table 18.

Test Methods

Tack: The tack was measured by the ball rolling method described in JISZ-0237.

Adhesion: The 180° peeling adhesion as defined in JIS Z-0237 (adherends:stainless steel plates; g/25 mm) was measured. The adhesion withpolyethylene plates as adherends was also measured by the same method.

Holding power: A load of 1 kg was applied to the 20 mm×20 mm adhesionarea at 40° C. in accordance with the method prescribed in JIS Z-0237,and the holding time or the slippage distance after a certain period oftime was measured.

                  TABLE 18                                                        ______________________________________                                        Aqueous            Adhesion                                                   cross-                     Stain-                                                                              Poly-                                        linkable                   less  ethyl-                                       resin dis-                                                                            Storage            steel ene   Holding                                persion No.                                                                           conditions* Tack   sheet sheet power                                  ______________________________________                                        R-11    Ordinary    13     2390  1150  No slip-                                       temperature                    page after                                                                    3 hours                                        High tempera-                                                                             12     2320  1080  No slip-                                       ture high                      page after                                     humidity                       3 hours                                R-12    Ordinary    12     2010  970   No slip-                                       temperature                    page after                                                                    3 hours                                        High tempera-                                                                             11     1920  950   No slip-                                       ture high                      page after                                     humidity                       3 hours                                R-13    Ordinary    13     2700  1210  No slip-                                       temperature                    page after                                                                    3 hours                                        High tempera-                                                                             13     2710  1200  No slip-                                       ture high                      page after                                     humidity                       3 hours                                r-4     Ordinary    11     1520  820   Falling                                (for    temperature                    after 2                                compari-                               minutes                                son)    High tempera-                                                                             3      190   50    Falling                                        ture high                      after 30                                       humidity                       minutes                                r-10    Ordinary    12     1930  920   Falling                                (for    temperature                    after 30                               compari-                               minutes                                son)    High tempera-                                                                             7      1010  530   Falling                                        ture high                      after 5                                        humidity                       minutes                                ______________________________________                                    

* The storage was carried out as follows: The aqueous crosslinkableresin dispersion to be tested was applied to a release paper and dried.Onto the resulting layer, a coat paper sheet was placed in close contactwith said layer. For testing at ordinary temperature, the assembly wasallowed to stand at 23° C. and 65% RH for 1 day prior to testing and,for testing after exposure to high-temperature, high-humidityconditions, the assembly was allowed to stand at 50° C. and 95% RH for10 days and then at 23° C. and 65% RH for 1 day.

EXAMPLE 66

The aqueous crosslinkable resin dispersions were each applied to an OPP(oriented polypropylene) film (1 cm×15 cm) to a dry film thickness of 15μm and dried at 105° C. for 2 minutes to give an adhesive tape. This wasapplied to a stainless steel plate, the whole was immersed in tap waterat 40° C. for 5 days and then evaluated for the extent of whitening orblushing. The results are shown in Table 19.

                  TABLE 19                                                        ______________________________________                                        Aqueous crosslink-                                                            able resin                                                                    dispersion No. Extent of whitening                                            ______________________________________                                        R-11           No whitening                                                   R-12           Slight whitening in edge portions                              R-13           No whitening                                                   r-4            Intense whitening in edge portions                             (for comparison)                                                                             and overall slight whitening                                   r-10           Somewhat intense whitening in edge                             (for comparison)                                                                             portions and overall slight whitening                          ______________________________________                                    

EXAMPLE 67 Binders for Heat-Sensitive Recording Paper

The aqueous dispersions and so forth were diluted with water to aconcentration of 10% and the dilutions were used as binders in thefollowing liquid compositions A, B and C:

    ______________________________________                                        "Liquid composition A"                                                        3-N-methyl-N-cyclohexylamino-6-methyl-7-anilino-                                                         300 parts                                          fluoran                                                                       10% Dispersion             300 parts                                          Water                      400 parts                                          "Liquid composition B"                                                        4,4'-Isopropylidenebis(2,6-dibromophenol)                                                                300 parts                                          10% Dispersion             200 parts                                          Water                      400 parts                                          "Liquid composition C"                                                        di-o-chlorophenyl adipate  100 parts                                          Calcium carbonate          300 parts                                          10% Dispersion             200 parts                                          Water                      300 parts                                          ______________________________________                                    

The above compositions were each made up into a dispersion by means of asand grinder until the particle size reached 0.8±0.1 μm. Then, 20 partsof liquid composition A, 70 parts of liquid composition B and 10 partsof liquid composition C, each in the form of a dispersion, were blendedand the thus-prepared coating liquid for forming a heat-sensitivecolor-developing layer was applied to a commercial fine paper basisweight of 55 g/m² to a dry coating weight of 6 g/m² by means of a wirebar and then dried to give a heat-sensitive recording paper.

The heat-sensitive recording papers obtained in the above manner weretested for sticking resistance and water resistance. The resultsobtained are shown in Table 20. The sticking resistance was evaluatedusing a Toshiba Medical model TP8300 printer for ultrasonographyaccording to the following criteria:

5: No sticking sound.

4: Almost no sticking sound.

3: Soft sticking sound.

2: Big sticking sound; the coat film is not taken up by the head.

1: Big sticking sound; the coat film is taken up by the head.

For water resistance evaluation, water was dropped on the boundarybetween the color-developed portion (black) and undeveloped portion, theboundary portion was rubbed with a finger, and the extent of migrationof the dye from the color-developed portion was investigated. Thesymbols ◯, Δ and × used in the table respectively have the followingmeanings:

◯: No dissolution from the color-developed portion.

Δ: Slight dissolution from the color-developed portion.

×: Much dissolution from the color-developed portion.

                  TABLE 20                                                        ______________________________________                                        Aqueous dispersion etc.                                                                           Sticking Water                                            No.                 resistance                                                                             resistance                                       ______________________________________                                        Aqueous crosslinkable resin                                                                       3        Δ                                          dispersion R-14                                                               Aqueous crosslinkable resin                                                                       4        ∘-Δ                            dispersion R-16                                                               Aqueous crosslinkable resin                                                                       5        ∘-Δ                            dispersion R-22                                                               Aqueous composition L-5                                                                           4        ∘-Δ                            Aqueous resin       4        ∘-Δ                            composition M-4                                                               Aqueous resin       4        ∘-Δ                            composition M-5                                                               Aqueous resin       4        ∘                                    composition M-9                                                               Water-dispersion    5        ∘                                    composition N-4                                                               Water-dispersion    5        ∘                                    composition N-5                                                               Aqueous resin dispersion                                                                          1        x                                                (for comparison) r-5                                                          Aqueous resin dispersion                                                                          1        Δ-x                                        (for comparison) r-11                                                         ______________________________________                                    

What is claimed is:
 1. An aqueous crosslinkable resin dispersioncharacterized by its being obtained by emulsion-polymerizing in anaqueous medium a monomer composition I composed of 0.1-40% by weight ofat least one polymerizable monomer (a) having, within its molecularstructure, a polymerizable double bond and an epoxy, aziridine oroxazoline group and 60-99.9% by weight of one or more otherpolymerizable monomers (b) copolymerizable with the polymerizablemonomer (a), the sum total of the polymerizable monomers (a) and (b)being 100% by weight, in the presence of a water-soluble orwater-dispersible emulsifier or emulsifiers selected from either one orboth of the groups (P) and (Q) below:(P) polymers IIa having a terminalalkylthio group and an acid value of not less than 200 obtained bypolymerizing a polymerizable monomer composition A containing anunsaturated carboxylic acid as an essential component thereof, in thepresence of an alkylmercaptan B having 6-18 carbon atoms, or saltsthereof; (Q) polymers IIb having a terminal alkylthio group and an acidvalue of not less than 200 obtained by polymerizing a polymerizablemonomer composition A containing an unsaturated carboxylic acid as anessential component thereof, in the presence of an alkylmercaptan Bhaving 6-18 carbon atoms, and further reacting the resulting polymerwith at least one polymerizable monomer (c) having, within its molecularstructure, a group reactive with a carboxyl group, or salts thereof. 2.An aqueous crosslinkable resin dispersion as claimed in claim 1, whereinthe emulsifier or emulsifiers have a R₁ S-- group, wherein R₁ is a C₆₋₁₈alkyl group, at one end of the molecular structure and a --H at theother end of the molecular structure and wherein the emulsifier oremulsifiers comprise repeating units of the formulas ##STR5## wherein R₂-R₈ are, independently in each repeating unit, hydrogen, halogen,methyl, carboxyl, alkoxycarbonyl or COO⁻ M⁺, wherein M⁺ is an ammoniumcation, an amine cation, an alkali metal cation or 1/2M1⁺, where M1⁺ isan alkaline earth metal cation, X⁺ is, independently in each repeatingunit, an ammonium cation, an amine cation, an alkali metal cation or1/2M1⁺, where M1⁺ is an alkaline earth metal cation, Y is a group havinga polymerizable unsaturated bond, Z is cyano, phenyl, substitutedphenyl, amido, N-mono- or N,N-disubstituted amido, alkoxycarbonyl or agroup of the formula --COO--(R₉ --O--)_(n) H, where R₉ is C₂₋₄ alkyleneand n is an integer of 1-50, said repeating units T, U, V and W beingarranged in an optional order provided that the following numericalconditions are satisfied:the number of occurrences of T and the numberof occurrences of U are each, independently, 0 or 1-500, with the totalnumber of T and U occurrences being 1-500, the number of occurrences ofV is 0 or 1-100 and the number of occurrences of W is 0 or 1-250.
 3. Anaqueous crosslinkable resin dispersion as claimed in claim 2, whereinthe emulsifier or emulsifiers used have R₁ S-- at one end of theirmolecule and --H at the other and comprises repeating units of theformulas ##STR6## in which R₁ to R₈, X, Y and Z are as defined above,said repeating units T, U, V and W being arranged in an optional orderprovided that the following numerical conditions are satisfied: that thenumber of occurrences of T and the number of occurrences of U are each 1to 499, with a total number of occurrences of T and U of 2 to 500, thatthe number of occurrences of V is 0 or 1 to 100 and that the number ofoccurrences of W is 0 or 1 to
 250. 4. An aqueous crosslinkable resindispersion as claimed in claim 1, wherein the other polymerizablemonomers (b) comprise at least one organosilane monomer having, withinits molecule, a polymerizable unsaturated group and at least onehydrolyzable group directly bound to the silicon atom.
 5. An aqueous,crosslinkable resin dispersion as claimed in claim 1, wherein a polymerselected from the group (Q) is used as the emulsifier.
 6. An aqueouscrosslinkable resin dispersion as claimed in claim 1, wherein theemulsifier or emulsifiers are used in an amount of 0.5 to 20 parts byweight per 100 parts by weight of the monomer composition [I].
 7. Anaqueous crosslinkable resin dispersion as claimed in claim 1, whereinthe polymerizable monomer or monomers (a) are used in an amount of 0.5to 20% by weight.
 8. A method of producing aqueous crosslinkable resindispersions which comprises emulsion-polymerizing in an aqueous medium amonomer composition I composed of 0.1-40% by weight of at least onepolymerizable monomer (a) having, within its molecule, a polymerizabledouble bond and an epoxy, aziridine or oxazoline group and 60-99.9% byweight of one or more other polymerizable monomers (b) copolymerizablewith the polymerizable monomer (a), the sum total of the polymerizablemonomers (a) and (b) being 100% by weight, in the presence of awater-soluble or water-dispersible emulsifier or emulsifiers selectedfrom either one or both of the groups (P) and (Q) mentioned below:(P)Polymers IIa having a terminal alkylthio group and an acid value of notless than 200 obtained by polymerizing a polymerizable monomercomposition A containing an unsaturated carboxylic acid as an essentialcomponent thereof in the presence of an alkylmercaptan B having 6 to 18carbon atoms, or salts thereof; (Q) Polymers IIb having a terminalalkylthio group and an acid value of not less 200 obtained bypolymerizing a polymerizable monomer composition A containing anunsaturated carboxylic acid as an essential component thereof in thepresence of an alkylmercaptan B having 6 to 18 carbon atoms and furtherreacting the resulting polymer with at least one polymerizable monomer(c) having, within its molecule, a group reactive with a carboxyl group,or salts thereof.
 9. A method of producing aqueous crosslinkable resindispersions as claimed in claim 8, wherein the emulsifier or emulsifiersused have R₁ S-- at one end of their molecule and --H at the other andcomprises repeating units of the formulas ##STR7## in which R₁ to R₈are, independently in each repeating unit, hydrogen, halogen, methyl,carboxyl, alkoxycarbonyl or COO⁻ M⁺, wherein M⁺ is an ammonium cation,an amine cation, an alkali metal cation or 1/2M1⁺, where M1⁺ is analkaline earth metal cation, X⁺ is, independently in each repeatingunit, an ammonium cation, an amine cation, an alkali metal cation or1/2M1⁺, where M1⁺ is an alkaline earth metal cation, Y is a group havinga polymerizable unsaturated bond, Z is cyano, phenyl, substitutedphenyl, amido, N-mono- or N,N-disubstituted amido, alkoxycarbonyl or agroup of the formula --COO--(R₉ --O--)_(n) H, where R₉ is C₂₋₄ alkyleneand n is an integer of 1-50, said repeating units T, U, V and W beingarranged in an optional order provided that the following numericalconditions are satisfied: that the number of occurrences of T and thenumber of occurrences of U are each independently 0 or 1 to 500, with atotal number of occurrences of T and U of 1 to 500, that the number ofoccurrences of V is 0 or 1 to 100 and that the number of occurrences ofW is 0 or 1 to
 250. 10. A method of producing aqueous crosslinkableresin dispersions as claimed in claim 8, wherein the emulsifier oremulsifiers used have R₁ S-- at one end of their molecule and --H at theother and comprises repeating units of the formulas ##STR8## in which R₁to R₈ are, independently in each repeating unit, hydrogen, halogen,methyl, carboxyl, alkoxycarbonyl or COO⁻ M⁺, wherein M⁺ is an ammoniumcation, an amine cation, an alkali metal cation or 1/2M1⁺, where M1⁺ isan alkaline earth metal cation, X⁺ is, independently in each repeatingunit, an ammonium cation, an amine cation, an alkali metal cation or1/2M1⁺, where M1⁺ is an alkaline earth metal cation, Y is a group havinga polymerizable unsaturated bond, Z is cyano, phenyl, substitutedphenyl, amido, N-mono- or N,N-disubstituted amido, alkoxycarbonyl or agroup of the formula --COO--(R₉ --O--)_(n) H, where R₉ is C₂₋₄ alkyleneand n is an integer of 1-50, said repeating units T, U, V and W beingarranged in an optional order provided that the following numericalconditions are satisfied: that the number of occurrences of t and thenumber of occurrences of U are each 1 to 499, with a total number ofoccurrences of T and U of 2 to 500, that the number of occurrences of Vis 0 or 1 to 100 and that the number of occurrences of W is 0 or 1 to250.
 11. A method of producing aqueous crosslinkable resin dispersionsas claimed in claim 8, wherein the monomer composition I is divided intotwo or more portions differing in composition from one another and theseportions are fed in sequence, so that the polymerization is carried outin the manner of multistep polymerization.
 12. A method of producingaqueous crosslinkable resin dispersions as claimed in claim 1, whereinat least two of the divided portions differ in the content ofpolymerizable monomer or monomers (a) from each other.
 13. A method ofproducing aqueous crosslinkable resin dispersions as claimed in claim11, wherein at least one of the divided portions does not contain anypolymerizable monomers (a).
 14. A method of producing aqueouscrosslinkable resin dispersions as claimed in claim 13, wherein thedivided portion which does not contain any polymerizable monomers (a) issubjected to polymerization in the last step.
 15. An aqueous compositionwhich comprises 100 parts by weight (on the solids basis) of an aqueouscrosslinkable resin dispersion as claimed in claim 1 and 1 to 200 partsby weight of a metal oxide or metal hydroxide or mixture thereof in theform of fine particles.
 16. An aqueous composition which comprises 100parts by weight (on the solids basis) of an aqueous crosslinkable resindispersion as claimed in claim 4 and 1 to 200 parts by weight of a metaloxide or metal hydroxide or mixture thereof in the form of fineparticles.
 17. An aqueous composition as claimed in claim 16, whereinthe metal oxide or metal hydroxide or mixture thereof in the form offine particles is aqueous colloidal silica.
 18. An aqueous resincomposition which comprises 100 parts by weight (on the solids basis) ofan aqueous crosslinkable resin dispersion as claimed in claim 1 and0.001 to 100 parts by weight of a water-soluble resin.
 19. An aqueousresin composition as claimed in claim 18, wherein the water-solubleresin is polyvinyl alcohol.
 20. An aqueous resin composition as claimedin claim 19, wherein the aqueous resin dispersion is obtained byemulsion polymerization in the presence of polyvinyl alcohol.
 21. Anaqueous resin composition as claimed in claim 19 as obtained by reactingthe aqueous crosslinkable resin dispersion and polyvinyl alcohol in thepresence of a radical polymerization catalyst.
 22. A water-dispersiblecomposition which comprises 100 parts by weight (on the solids basis) ofan aqueous crosslinkable resin dispersion as claimed in claim 1, 1-200parts by weight, of a metal oxide or metal hydroxide or mixture thereofin the form of fine particles and 0.001 to 100 parts by weight of awater-soluble resin.
 23. A coating composition which contains an aqueouscrosslinkable resin dispersion as claimed in claim
 1. 24. A coatingcomposition as claimed in claim 23, which further contains a metal oxideor metal hydroxide or mixture thereof in the form of fine particles. 25.A coating composition as claimed in claim 24, wherein the metal oxide ormetal hydroxide or mixture thereof in the form of fine particles isaqueous colloidal silica.
 26. A coating composition as claimed in claim25, which further contains a water-soluble resin.
 27. A coatingcomposition as claimed in claim 26, wherein the water-soluble resin ispolyvinyl alcohol.
 28. A coating composition as claimed in claim 26,which further contains a metal oxide or metal hydroxide or mixture inthe form of fine particles.
 29. A coating composition which comprises anaqueous crosslinkable resin dispersion as claimed in claim
 4. 30. Acoating composition as claimed in claim 29, which further contains acrosslinking agent.
 31. A coating composition as claimed in claim 30,which further contains a filler.
 32. An adhesive which contains anaqueous crosslinkable resin dispersion as claimed in claim
 1. 33. Anadhesive as claimed in claim 32, which further contains a metal oxide ormetal hydroxide or mixture thereof in the form of fine particles.
 34. Anadhesive as claimed in claim 33, wherein the metal oxide and/or metalhydroxide in the form of fine particles is aqueous colloidal silica. 35.An adhesive as claimed in claim 34, which further contains awater-soluble resin.
 36. An adhesive as claimed in claim 35, wherein thewater-soluble resin is polyvinyl alcohol.
 37. An adhesive as claimed inclaim 35, which further contains a metal oxide or metal hydroxide ormixture thereof in the form of fine particles.
 38. An adhesive asclaimed in any one of claims 32-37, wherein the polymer obtained bypolymerizing the monomer composition I has a glass transitiontemperature within the range of -80° C. to 0° C.
 39. A coatingcomposition for heat-sensitive color-developing layer formation whichcontains an aqueous crosslinkable resion dispersion as claimed in claim1 together with heat-sensitive color-developing components.
 40. Acoating composition for heat-sensitive color-developing layer formationas claimed in claim 39, which further contains a metal oxide or metalhydroxide or mixture thereof in the form of fine particles.
 41. Acoating composition for heat-sensitive color-developing layer formationas claimed in claim 40, wherein the metal oxide or metal hydroxide ormixture thereof in the form of fine particles is aqueous colloidalsilica.
 42. coating composition for heat-sensitive color-developinglayer formation as claimed in claim 41, which further contains awater-soluble resin.
 43. A coating composition for heat-sensitivecolor-developing layer formation as claimed in claim 42, wherein thewater-soluble resin is polyvinyl alcohol.
 44. A coating composition forheat-sensitive color-developing layer formation as claimed in claim 42or 43, which further contains a metal oxide or metal hydroxide ormixture thereof in the form of fine particles.
 45. A coating compositionfor pressure-sensitive color-developing layer formation which containsan aqueous crosslinkable resin dispersion as claimed in claim 1 togetherwith pressure-sensitive color-developing components.